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.

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

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...

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.

Olefin metathesis and metathesis polymerization

CERN Document Server

Ivin, K J

1997-01-01

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

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

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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.

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

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Sambasivarao Kotha

2015-08-01

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

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.

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

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Shawna L. Balof

2015-10-01

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

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.

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).

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.

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.

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.

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

KAUST Repository

Poater, Albert; Cavallo, Luigi

2015-01-01

During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

KAUST Repository

Poater, Albert

2015-09-29

During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

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

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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.

Olefin metathesis in nano-sized systems

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Denise Méry

2011-01-01

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

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

Directory of Open Access Journals (Sweden)

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.

Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

Science.gov (United States)

Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

2014-10-15

TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH.

Science.gov (United States)

Zhang, Jing; Zhang, Ying; Wang, Hui; Guan, Xiaohong

2014-07-01

Ru(III) was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru(III) could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru(III) catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru(III), respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru(III) catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant (ktapp) decreased from 643.20 to 2.67 (mol/L)⁻¹sec⁻¹ with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru(III), as an electron shuttle, was oxidized by permanganate to Ru(VI) and Ru(VII), which acted the co-oxidants for decomposition of aniline. Although Ru(III) could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru(III) into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru(III) toward permanganate oxidation in our future study. Copyright © 2014. Published by Elsevier B.V.

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.

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

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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.

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.

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.

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.

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.

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

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....

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.

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...

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

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

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

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.

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

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

Directory of Open Access Journals (Sweden)

Thibault E. Schmid

2015-09-01

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

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.

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.

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.

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.

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...

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.

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.

Ru (III) Catalyzed Oxidation of Aliphatic Ketones by N-Bromosuccinimide in Aqueous Acetic Acid: A Kinetic Study

Science.gov (United States)

Giridhar Reddy, P.; Ramesh, K.; Shylaja, S.; Rajanna, K. C.; Kandlikar, S.

2012-01-01

Kinetics of Ru (III) catalyzed oxidation of aliphatic ketones such as acetone, ethyl methyl ketone, diethyl ketone, iso-butylmethyl ketone by N-bromosuccinimide in the presence of Hg(II) acetate have been studied in aqueous acid medium. The order of [N-bromosuccinimide] was found to be zero both in catalyzed as well as uncatalyzed reactions. However, the order of [ketone] changed from unity to a fractional one in the presence of Ru (III). On the basis of kinetic features, the probable mechanisms are discussed and individual rate parameters evaluated. PMID:22654610

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.

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.

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...

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...

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)

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.

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.

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...

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.

{sup 96}Ru(p,{gamma}){sup 97}Rh measurement at the GSI storage ring

Energy Technology Data Exchange (ETDEWEB)

Zhong, Q; Aumann, T; Boretzky, K; Bosch, F; Braeuning, H; Brandau, C; Ershova, O; Geissel, H; Heil, M; Kelic, A; Kozhuharov, C; Langer, C; Bleis, T Le; Litvinov, Y A [GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, Darmstadt, 64291 (Germany); Bishop, S; Dillmann, I [Technische Universitaet Muenchen, 85748 Garching (Germany); Blaum, K [Max-Planck-Institut fuer Kernphysik, 69117 Heidelberg (Germany); Davinson, T [University of Edinburgh, Edinburgh (United Kingdom); Gyuerky, G [Institute of Nuclear Research of the Hungarian Academy of Sciences (Hungary); Kaeppeler, F, E-mail: r.reifarth@gsi.d [Forschungszentrum Karlsruhe, Institut fuer Kernphysik, Karlsruhe (Germany)

2010-01-01

A pioneering experiment was recently performed at the Experimental Storage Ring (ESR) at GSI. Fully stripped ions of {sup 96}Ru were injected into the storage ring and slowed down to a few MeV per nucleon. The {sup 97}Rh ions from the {sup 96}Ru(p,{gamma}) reaction at a newly developed hydrogen jet target were detected with Double Sided Silicon Strip Detectors (DSSSD) mounted inside a pocket. The experiment and the status of the analysis at a beam energy of 11 MeV per nucleon will be presented.

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.

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.

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

Indian Academy of Sciences (India)

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

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.

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

Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo Compounds: Formation of Olefins from Two Different Carbene Precursors.

Science.gov (United States)

Wang, Bo; Yi, Heng; Zhang, Hang; Sun, Tong; Zhang, Yan; Wang, Jianbo

2018-01-19

Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein, we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been experimentally demonstrated that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.

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.

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.

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.

Novel Platinum-Catalyzed Ring-Opening of 1,2-Cyclopropanated Sugars with Alcohols

DEFF Research Database (Denmark)

Beyer, Jürgen; Madsen, Robert

1998-01-01

Reaction of 1,2-cyclopropanated sugars with a catalytic amount ofZeise's dimer [Pt(C2H4)Cl2]2 and an alcohol gives 2-C-branched glycosides by a novel platinum catalyzed ring-opening. A wide variety of alcohols can participate in this ring-opening reaction giving 2-C-branched glycosides ranging from...

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.

Reactions of ethyl diazoacetate catalyzed by methylrhenium trioxide

Energy Technology Data Exchange (ETDEWEB)

Zhu, Z.; Espenson, H. [Iowa State Univ., Ames, IA (United States)

1995-11-03

Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) has found wise use in catalysis, including the epoxidation and metathesis of olefins, aldehyde olefination, and oxygen transfer. Extensive reports have now appeared in the area of MTO-catalyzed substrate oxidations with hydrogen peroxide. Certain catalytic applications of MTO for organic reactions that do not utilize peroxide have now been realized. In particular, a catalytic amount of MTO with ethyl diazoacetate (EDA) will convert aromatic imines to aziridines and convert aldehydes and ketones to epoxides. The aziridine preparation proceeds in high yields under anaerobic conditions more conveniently than with existing methods. Compounds with a three-membered heterocyclic ring can be obtained with the EDA/MTO catalytic system. Aromatic imines undergo cycloaddition reactions to give aziridines under mild conditions.

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.

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...

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

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

DEFF Research Database (Denmark)

Poulsen, Carina Storm; Madsen, Robert

2002-01-01

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

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

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

KAUST Repository

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

2010-01-01

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

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

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.

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.

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.

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

KAUST Repository

Baumgartner, Corinne

2010-01-01

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

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

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.

Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene with alcohols

Directory of Open Access Journals (Sweden)

Katrina Tait

2016-10-01

Full Text Available Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene derivatives using alcohol nucleophiles were investigated. The optimal conditions were found to be 10 mol % PdCl2(CH3CN2 in methanol, offering yields up to 92%. The reaction was successful using primary, secondary and tertiary alcohol nucleophiles and was compatible with a variety of substituents on cyclopropanated oxabenzonorbornadiene. With unsymmetrical C1-substituted cyclopropanated 7-oxabenzonorbornadienes, the regioselectivity of the reaction was excellent, forming only one regioisomer in all cases.

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.

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.

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.

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.

Lipase-catalyzed ring-opening polymerization of lactones to polyesters and its mechanistic aspects.

Science.gov (United States)

Namekawa, S; Suda, S; Uyama, H; Kobayashi, S

1999-01-01

Lipase catalysis induced a ring-opening polymerization of lactones with different ring-sizes. Small-size (four-membered) and medium-size lactones (six- and seven-membered) as well as macrolides (12-, 13-, 16-, and 17-membered) were subjected to lipase-catalyzed polymerization. The polymerization behaviors depended primarily on the lipase origin and the monomer structure. The macrolides showing much lower anionic polymerizability were enzymatically polymerized faster than epsilon-caprolactone. The granular immobilized lipase derived from Candida antartica showed extremely efficient catalysis in the polymerization of epsilon-caprolactone. Single-step terminal functionalization of the polyester was achieved by initiator and terminator methods. The enzymatic polymerizability of lactones was quantitatively evaluated by Michaelis-Menten kinetics.

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.

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

Science.gov (United States)

Ducrot, Aurélien B; Coulson, Ben A; Perutz, Robin N; Duhme-Klair, Anne-Kathrin

2016-12-19

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy) 2 (L 2 )MoO 2 (solv)] 2+ were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy) 2 (phen-NH 2 )] 2+ , while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy) 2 (H 2 -L 2 )] 2+ . In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center

Lipase catalyzed HEMA initiated ring-opening polymerization: In situ formation of mixed polyester methacrylates by transesterification

NARCIS (Netherlands)

Takwa, M.; Xiao, Y.; Simpson, N.; Malmstrom, E.; Hult, K.; Koning, C.E.; Heise, A.; Martinelle, M.

2008-01-01

2-Hydroxyethyl methacrylate (HEMA) was used as initiator for the enzymatic ring-opening polymerization (ROP) of ¿-pentadecalactone (PDL) and e-caprolactone (CL). The lipase B from Candida antarctica was found to catalyze the cleavage of the ester bond in the HEMA end group of the formed polyesters,

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

Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles.

Science.gov (United States)

Zhang, Qing-Wei; An, Kun; Liu, Li-Chuan; Yue, Yuan; He, Wei

2015-06-01

Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

International Nuclear Information System (INIS)

Wang, Xue; Lee, Yong Rok

2013-01-01

Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings

Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

Energy Technology Data Exchange (ETDEWEB)

Wang, Xue; Lee, Yong Rok [Yeungnam Univ., Gyeongsan (Korea, Republic of)

2013-06-15

Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings.

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

(Salen)Ti(Ⅳ)-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

Institute of Scientific and Technical Information of China (English)

Zheng Hong ZHOU; Zhao Ming LI; Bing LIU; Kang Ying LI; Li Xin WANG; Guo Feng ZHAO; Qi Lin ZHOU; Chu Chi TANG

2006-01-01

The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a (salen)Ti(Ⅳ) complex formed in situ from the reaction of Ti(OPr-i)4 and the chiral Schiff base derived from (1R,2R)-(+)-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity (up to 73% ee).

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.

A rechargeable hydrogen battery based on Ru catalysis.

Science.gov (United States)

Hsu, Shih-Fan; Rommel, Susanne; Eversfield, Philipp; Muller, Keven; Klemm, Elias; Thiel, Werner R; Plietker, Bernd

2014-07-01

Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H2 battery which is based on the principle of the Ru-catalyzed hydrogenation of CO2 to formic acid (charging process) and the Ru-catalyzed decomposition of formic acid to CO2 and H2 (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure-free conditions (discharging process). Up to five charging-discharging cycles were performed without decrease of storage capacity. The resulting CO2/H2 mixture is free of CO and can be employed directly in fuel-cell technology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Zirconium(IV)-Catalyzed Ring Opening of on-DNA Epoxides in Water.

Science.gov (United States)

Fan, Lijun; Davie, Christopher P

2017-05-04

DNA-encoded library technology (ELT) has spurred wide interest in the pharmaceutical industry as a powerful tool for hit and lead generation. In recent years a number of "DNA-compatible" chemical modifications have been published and used to synthesize vastly diverse screening libraries. Herein we report a newly developed, zirconium tetrakis(dodecyl sulfate) [Zr(DS) 4 ] catalyzed ring-opening of on-DNA epoxides in water with amines, including anilines. Subsequent cyclization of the resulting on-DNA β-amino alcohols leads to a variety of biologically interesting, nonaromatic heterocycles. Under these conditions, a library of 137 million on-DNA β-amino alcohols and their cyclization products was assembled. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Sociolinguistic Analysis of Metathesis in Azeri Language

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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....

Atomic scale insights into electrochemical versus gas phase oxidation of HCl over RuO2-based catalysts: A comparative review

International Nuclear Information System (INIS)

Over, Herbert

2013-01-01

In this article our current understanding of the electro-catalyzed chlorine evolution reaction (CER) in comparison with that of the heterogeneously-catalyzed gas phase oxidation of HCl (Deacon process: heterogeneous catalysis) over RuO 2 -based catalysts will be reviewed. Both types of harsh reactions are chemically similar: The main concern is catalyst stability, and in both cases the best catalyst contains RuO 2 as the catalytically active component so that a critical comparison may provide new insights into the underlying physicochemical processes. It is the primary scope of this review addresses atomic scale information on the RuO 2 -catalyzed HCl oxidation reaction either in electrochemical or in gas phase environment. In particular, the involved reaction mechanisms and the reason for the extraordinary stability of RuO 2 under such harsh reaction conditions will be discussed, emphasizing similarities and differences in the Deacon process and the CER and what can be learnt from this comparison. The distinct properties of RuO 2 , which are responsible for its extraordinary catalytic performance in both the CER and the Deacon process, are highlighted

{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.

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.

Mixed phase Pt-Ru catalyst for direct methanol fuel cell anode by flame aerosol synthesis

DEFF Research Database (Denmark)

Chakraborty, Debasish; Bischoff, H.; Chorkendorff, Ib

2005-01-01

A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst wa......Ru1/Vulcan carbon. The kinetics of methanol oxidation on the mixed phase catalyst was also explored by electrochemical impedance spectroscopy. (c) 2005 The Electrochemical Society.......A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst...... was found to be a mixture of nanocrystalline, mostly unalloyed Pt and an amorphous phase mostly of Ru and to a lesser extent of Pt oxides on top of the crystalline phase. The flame-produced Pt1Ru1 demonstrated similar onset potential but similar to 60% higher activity compared to commercially available Pt1...

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.

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.

Towards identifying the active sites on RuO2(110) in catalyzing oxygen evolution  

DEFF Research Database (Denmark)

Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen

2017-01-01

While the surface atomic structure of RuO2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determ......While the surface atomic structure of RuO2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used...... on the coordinatively unsaturated Ru sites (CUS) and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential...

Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

Science.gov (United States)

Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

2015-07-21

The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven

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%.

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 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.

Orientation-Dependent Oxygen Evolution on RuO₂ without Lattice Exchange

DEFF Research Database (Denmark)

Stoerzinger, Kelsey A.; Diaz-Morales, Oscar; Kolb, Manuel

2017-01-01

the potential involvement of lattice oxygen in the OER mechanism with online electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO2 films and particles, in contrast to previous...... work, suggesting lattice oxygen is not exchanged in catalyzing OER on crystalline RuO2 surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by density functional theory, where more active facets bind oxygen more weakly. This new...

Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Han, Yong; Evans, James W. [Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011, USA and Ames Laboratory—U.S. Department of Energy, Iowa State University, Ames, Iowa 50011 (United States)

2015-10-28

Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C{sub 6}-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ∼0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. This in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001)

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.

Orientation-Dependent Oxygen Evolution on RuO ₂ without Lattice Exchange

Energy Technology Data Exchange (ETDEWEB)

Stoerzinger, Kelsey A.; Diaz-Morales, Oscar; Kolb, Manuel; Rao, Reshma R.; Frydendal, Rasmus; Qiao, Liang; Wang, Xiao Renshaw; Halck, Niels Bendtsen; Rossmeisl, Jan; Hansen, Heine A.; Vegge, Tejs; Stephens, Ifan E. L.; Koper, Marc T. M.; Shao-Horn, Yang

2017-03-15

RuO2 catalysts exhibit record activities towards the oxygen evolution reaction (OER), which is crucial to enable efficient and sustainable energy storage. Here we examine the RuO2 OER kinetics on rutile (110), (100), (101), and (111) orientations, finding (100) the most active. We assess the potential involvement of lattice oxygen in the OER mechanism with online 3 electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO2 films and particles, in contrast to previous work, suggesting lattice oxygen is not exchanged in catalyzing OER on crystalline RuO2 surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by DFT, where more active facets bind oxygen more weakly. This new understanding of the active sites provides a design strategy to enhance the OER activity of RuO2 nanoparticles by facet engineering.

RuPd, RuCo, PdCo and RuPdCo materials as candidates for cathode catalyzers in PEM fuel cells; Materiales RuPd, RuCo, PdCo y RuPdCo como candidatos a catalizadores catodicos en celdas de combustible tipo PEM

Energy Technology Data Exchange (ETDEWEB)

Leyva Noyola, Fatima; Solorza Feria, Omar [Centro de Investigacion y Estudios Superiores del IPN, Mexico, D.F. (Mexico)]. E-mail: fleyva@cinvestav.mx

2009-09-15

This work reports on the catalytic activity of RuPd, RuCo, PdCo and RuPdCo material for oxygen reduction reaction (ORR). These materials were synthesized using chemical reduction with NaBH{sub 4} as a reducing agent in THF, in ambient temperature and pressure conditions. The evaluation of the catalytic activity was done using cyclic voltamperometry (CV) and rotary disc electrode (RDE) in H{sub 2}SO{sub 4} 0.5 M. The kinetic results showed that the electrochemical reaction involves 4 electrons and the transfer of the first electron is the determinant stage. The values of {alpha}, i0 and the Tafel slope were very similar for the four materials studied, around 0.4, 5x10{sup -6} mA cm{sup -2} and 60 mV dec-1, respectively. Although these values are less than those reported for nanostructured platinum, they are better than those reported for other materials such as pure Pd, which enables them to be considered as cathode catalysts for a proton exchange membrane fuel cell. [Spanish] En este trabajo se reporta la actividad catalitica de los materiales RuPd, RuCo, PdCo y RuPdCo para la reaccion de reduccion de oxigeno (RRO). Estos materiales fueron sintetizados por el metodo de reduccion quimica, usando NaBH{sub 4} como agente reductor en THF, en condiciones de temperatura y presion ambiental. La evaluacion de la actividad catalitica fue realizada usando Voltamperometria Ciclica (VC) y Electrodo Disco Rotatorio (EDR) en H{sub 2}SO{sub 4} 0.5 M. Los resultados cineticos mostraron que la reaccion electroquimica procede por la via de 4 electrones y la etapa determinante es la transferencia del primer electron. Los valores de {alpha}, i0 y pendiente de Tafel fueron muy similares para los 4 materiales estudiados, siendo estos de alrededor de 0.4, 5x10{sup -6} mA cm{sup -2} y 60 mV dec{sup -1}, respectivamente. Sin embargo, aun cuando estos valores son menores que los reportados para platino nanoestructurado, son mejores que los reportados para otros materiales como el Pd puro

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.

The Formation of Pyrroline and Tetrahydropyridine Rings in Amino Acids Catalyzed by Pyrrolysine Synthase (PylD)

KAUST Repository

Quitterer, Felix

2014-06-10

The dehydrogenase PylD catalyzes the ultimate step of the pyrrolysine pathway by converting the isopeptide L-lysine-Nε-3R-methyl-D-ornithine to the 22nd proteinogenic amino acid. In this study, we demonstrate how PylD can be harnessed to oxidize various isopeptides to novel amino acids by combining chemical synthesis with enzyme kinetics and X-ray crystallography. The data enable a detailed description of the PylD reaction trajectory for the biosynthesis of pyrroline and tetrahydropyridine rings as constituents of pyrrolysine analogues. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium-catalyzed reactions--a treasure trove of atom-economic transformations.

Science.gov (United States)

Trost, Barry M; Frederiksen, Mathias U; Rudd, Michael T

2005-10-21

The demand for new chemicals spanning the fields of health care to materials science combined with the pressure to produce these substances in an environmentally benign fashion pose great challenges to the synthetic chemical community. The maximization of synthetic efficiency by the conversion of simple building blocks into complex targets remains a fundamental goal. In this context, ruthenium complexes catalyze a number of non-metathesis conversions and allow the rapid assembly of complex molecules with high selectivity and atom economy. These complexes often exhibit unusual reactivity. Careful consideration of the mechanistic underpinnings of the transformations can lead to the design of new reactions and the discovery of new reactivity.

Pd-RuSe/C as ORR specific catalyst in alkaline solution containing methanol

Energy Technology Data Exchange (ETDEWEB)

Maheswari, S.; Sridhar, P.; Pitchumani, S. [CSIR-Central Electrochemical Research Institute-Madras Unit, CSIR Complex, Chennai 600 113 (India)

2012-12-15

Carbon supported RuSe (RuSe/C) catalyst in varying atomic ratios of Ru to Se, namely, 1:1, 2:1, and 3:1 were prepared and their performances were compared with carbon supported Ru (Ru/C). Based on the performance, Palladium was incorporated into as prepared RuSe(2:1)/C and heat treated HTRuSe(2:1)/C. Ru/C, RuSe/C, and Pd-RuSe/C were characterized by X-ray diffraction (XRD) and transmission electron microscopy techniques. The XRD analyses of Ru/C, RuSe/C and Pd-HTRuSe/C show the formation of the hcp structure of Ru particles and the mean particle size was obtained from Ru(101) peak. The electrochemical characterizations of Ru/C, RuSe/C, Pd-HTRuSe(2:1)/C and Pd-RuSe(2:1)/C were conducted by cyclic voltammetry. Linear Sweep Voltammetric studies showed that incorporation of Pd in HTRu-Se(2:1)/C resulted in better catalytic activity toward oxygen reduction with resistance to methanol oxidation. The quantity of hydrogen peroxide produced was obtained from rotating ring disk electrode studies. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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.

Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

Energy Technology Data Exchange (ETDEWEB)

Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

2009-08-01

The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

Preparation of PtRu/Carbon hybrid materials by hydrothermal carbonization: A study of the Pt:Ru atomic ratio

International Nuclear Information System (INIS)

Tusi, Marcelo Marques; Brandalise, Michele; Correa, Olandir Vercino; Oliveira Neto, Almir; Linardi, Marcelo; Spinace, Estevam Vitorio; Villalba, Juan Carlo

2009-01-01

PtRu/Carbon materials with different Pt:Ru atomic ratios (30:70, 50:50, 60:40, 80:20 and 90:10) and 5 wt% of nominal metal load were prepared by hydrothermal carbonization using H 2 PtCl 6.6 H 2 O and RuCl 3. xH 2 O as metals sources and catalysts of the carbonization process and starch as carbon source and reducing agent. The obtained materials were treated at 900 deg C under argon and characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of methanol was studied by cyclic voltammetry and chronoamperometry using thin porous coating technique. The PtRu/Carbon materials showed Pt:Ru atomic ratios obtained by EDX similar to the nominal ones. XRD analysis showed that Pt face-cubic centered (FCC) and Ru hexagonal close-packed (HCP) phases coexist in the obtained materials. The average crystallite sizes of the Pt (FCC) phase were in the range of 8-12 nm. The material prepared with Pt:Ru atomic ratio of 50:50 showed the best performance for methanol electro-oxidation. (author)

Facile one-pot synthesis of 1-amido alkyl-2-naphthols by RuCl2(PPh3)3-catalyzed multi-component reactions

International Nuclear Information System (INIS)

Zhu, Xiaoyan; Lee, Yong Rok; Kim, Sung Hong

2012-01-01

We have developed an efficient and general synthesis of 1-amidoalkyl-2-naphthols by RuCl 2 (PPh 3 ) 3 -catalyzed one-pot multi-component reaction of 2-naphthol with aromatic aldehydes and amides. The advantages of these methodologies are easy handling, mild reaction conditions, and use of an effective and non-toxic catalyst. Molecules bearing 1,3-amino oxygenated functional groups have been reported to exhibit a variety of biological and pharmacological activities including nucleoside antibiotics and HIV protease inhibitors such as ritonavir and lipinavir. Importantly, 1-amidoalkyl-2-naphthols can be easily converted to biologically active 1-aminomethyl-2-naphthols by amide hydrolysis. These compounds also exhibit potent antihypertensive, adrenoceptor-blocking, and Ca +2 channel-blocking activities. Because of the importance of these compounds, numerous methods for the synthesis of 1-amidoalkyl-2-naphthols have been described. The reported methods mainly include one-pot three-component reactions of 2-naphthol, aromatic aldehydes, and amides

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution

Science.gov (United States)

Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-06-01

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy–carbon core–shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10–30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2–6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

A high-performance renewable thermosetting resin derived from eugenol.

Science.gov (United States)

Harvey, Benjamin G; Sahagun, Christopher M; Guenthner, Andrew J; Groshens, Thomas J; Cambrea, Lee R; Reams, Josiah T; Mabry, Joseph M

2014-07-01

A renewable bisphenol, 4,4'-(butane-1,4-diyl)bis(2-methoxyphenol), was synthesized on a preparative scale by a solvent-free, Ru-catalyzed olefin metathesis coupling reaction of eugenol followed by hydrogenation. After purification, the bisphenol was converted to a new bis(cyanate) ester by standard techniques. The bisphenol and cyanate ester were characterized rigorously by NMR spectroscopy and single-crystal X-ray diffraction studies. After complete cure, the cyanate ester exhibited thermal stability in excess of 350 °C and a glass transition temperature (Tg ) of 186 °C. As a result of the four-carbon chain between the aromatic rings, the thermoset displayed a water uptake of only 1.8% after a four day immersion in 85 °C water. The wet Tg of the material (167 °C) was only 19 °C lower than the dry Tg , and the material showed no significant degradation as a result of the water treatment. These results suggest that this resin is well suited for maritime environments and provide further evidence that full-performance resins can be generated from sustainable feedstocks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium-Catalyzed Transformations of Alcohols: Mechanistic Investigations and Methodology Development

DEFF Research Database (Denmark)

Makarov, Ilya; Madsen, Robert; Fristrup, Peter

with dimethoxyisopropylidene and pyridilidene ligands could be more active than RuCl2(IiPr)(p-cymene) used in the mechanistic investigation. Two analogs of the calculated complexes were synthesized but were not isolated in a pure form. The amidation reaction catalyzed by a mixture containing the N-ethyl pyridilidene...

π-face donation from the aromatic N-substituent of N-heterocyclic carbene ligands to metal and its role in catalysis

KAUST Repository

Credendino, Raffaele

2012-05-16

In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.

Electronic-level interactions of tungsten oxide with unsupported Se/Ru electrocatalytic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Lewera, Adam; Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Hunger, Ralf [Institute of Materials Science, Darmstadt University of Technology, Darmstadt (Germany); Kolary-Zurowska, Aneta [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Wieckowski, Andrzej [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL (United States); Kulesza, Pawel J., E-mail: pkulesza@chem.uw.edu.p [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

2010-11-01

Se/Ru nanoparticles - a potent non-platinum catalyst towards oxygen reduction reaction - were modified by hydrated WO{sub 3} and investigated using the rotating disk/ring electrode methods and by synchrotron X-ray photoelectron spectroscopy. The modification resulted in an enhanced catalytic activity towards oxygen reduction reaction (ORR). Our data indicate that the oxygen reduction current starts ca. 70 mV more positive and formation of undesirable hydrogen peroxide has significantly decreased following the modification of Se/Ru with WO{sub 3}. X-ray photoelectron spectroscopy reveals that WO{sub 3} interacts electronically with Se/Ru as the W 4f and Se 3d line-shapes change. We therefore conclude that the electronic interactions between Se/Ru and WO{sub 3} are primarily responsible for the increase in activity and selectivity of the WO{sub 3}-modified Se/Ru towards ORR.

Electronic-level interactions of tungsten oxide with unsupported Se/Ru electrocatalytic nanoparticles

International Nuclear Information System (INIS)

Lewera, Adam; Miecznikowski, Krzysztof; Hunger, Ralf; Kolary-Zurowska, Aneta; Wieckowski, Andrzej; Kulesza, Pawel J.

2010-01-01

Se/Ru nanoparticles - a potent non-platinum catalyst towards oxygen reduction reaction - were modified by hydrated WO 3 and investigated using the rotating disk/ring electrode methods and by synchrotron X-ray photoelectron spectroscopy. The modification resulted in an enhanced catalytic activity towards oxygen reduction reaction (ORR). Our data indicate that the oxygen reduction current starts ca. 70 mV more positive and formation of undesirable hydrogen peroxide has significantly decreased following the modification of Se/Ru with WO 3 . X-ray photoelectron spectroscopy reveals that WO 3 interacts electronically with Se/Ru as the W 4f and Se 3d line-shapes change. We therefore conclude that the electronic interactions between Se/Ru and WO 3 are primarily responsible for the increase in activity and selectivity of the WO 3 -modified Se/Ru towards ORR.

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.

Luminescent pH sensor of a novel imidazole-containing hexanuclear Ru(II) polypyridyl complex

Science.gov (United States)

Cheng, Feixiang; Tang, Ning; Chen, Jishu; Chen, Guang

2013-10-01

Hexapodal ligand H6L containing imidazole rings has been prepared by the reaction of 1,10-phenanthroline-5,6-dione with 1,2,3,4,5,6-hexakis[(3-formylphenoxy)methyl]benzene. The Ru(II) polypyridyl complex [{Ru(bpy)2}6(μ6-H6L)](PF6)12 (bpy = 2,2'-bipyridine) has been synthesized by the reaction of Ru(bpy)2Cl2·2H2O with ligand H6L. The pH effects on the UV-vis absorption and emission spectra of the complex have been studied. The ground- and excited-state ionization constants of the acid-base equilibria have been calculated according to the absorbance and emission data. The complex acts as an off-on-off luminescent pH sensor through two successive deprotonation processes of imidazole rings, with a maximum on-off ratio of 5 in buffer solution.

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

Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers

Directory of Open Access Journals (Sweden)

Simone Piccinin

2015-09-01

Full Text Available Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main structural and electronic molecular properties. In particular, we compare the thermodynamics of the water oxidation cycle for single-site Ru-POM and multiple-site Ru4-POM complexes. For the Ru-POM case, we also investigate the reaction free energy as a function of the Ru oxidation state. We find that the overpotential of these molecular catalysts is primarily determined by the oxidation state of the metal center and is minimum for Ru(IV. In solution, the number of active sites is shown to play a minor role on the reaction energetics. The results are rationalized and discussed in terms of the local structure around the active sites and of the electrostatic screening due to the molecular structure or the solvent.

Crystal structure of a mononuclear Ru(II) complex with a back-to-back terpyridine ligand: [RuCl(bpy)(tpy-tpy)](.).

Science.gov (United States)

Rein, Francisca N; Chen, Weizhong; Scott, Brian L; Rocha, Reginaldo C

2015-09-01

We report the structural characterization of [6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine](2,2'-bi-pyridine)-chlorido-ruthenium(II) hexa-fluorido-phosphate, [RuCl(C10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2'-bi-pyridine (bpy) and the tridendate ligand 6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine (tpy-tpy). The [RuCl(bpy)(tpy-tpy)](+) monocation has a distorted octa-hedral geometry at the central Ru(II) ion due to the restricted bite angle [159.32 (16)°] of the tridendate ligand. The Ru-bound tpy and bpy moieties are nearly planar and essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between the least-squares planes. The lengths of the two Ru-N bonds for bpy are 2.028 (4) and 2.075 (4) Å, with the shorter bond being opposite to Ru-Cl. For tpy-tpy, the mean Ru-N distance involving the outer N atoms trans to each other is 2.053 (8) Å, whereas the length of the much shorter bond involving the central N atom is 1.936 (4) Å. The Ru-Cl distance is 2.3982 (16) Å. The free uncoordinated moiety of tpy-tpy adopts a trans,trans conformation about the inter-annular C-C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant π-π stacking inter-actions based on tpy-tpy. The crystal structure reported here is the first for a tpy-tpy complex of ruthenium.

Formation and nitrile hydrogenation performance of Ru nanoparticles on a K-doped Al2O3 surface.

Science.gov (United States)

Muratsugu, Satoshi; Kityakarn, Sutasinee; Wang, Fei; Ishiguro, Nozomu; Kamachi, Takashi; Yoshizawa, Kazunari; Sekizawa, Oki; Uruga, Tomoya; Tada, Mizuki

2015-10-14

Decarbonylation-promoted Ru nanoparticle formation from Ru3(CO)12 on a basic K-doped Al2O3 surface was investigated by in situ FT-IR and in situ XAFS. Supported Ru3(CO)12 clusters on K-doped Al2O3 were converted stepwise to Ru nanoparticles, which catalyzed the selective hydrogenation of nitriles to the corresponding primary amines via initial decarbonylation, the nucleation of the Ru cluster core, and the growth of metallic Ru nanoparticles on the surface. As a result, small Ru nanoparticles, with an average diameter of less than 2 nm, were formed on the support and acted as efficient catalysts for nitrile hydrogenation at 343 K under hydrogen at atmospheric pressure. The structure and catalytic performance of Ru catalysts depended strongly on the type of oxide support, and the K-doped Al2O3 support acted as a good oxide for the selective nitrile hydrogenation without basic additives like ammonia. The activation of nitriles on the modelled Ru catalyst was also investigated by DFT calculations, and the adsorption structure of a nitrene-like intermediate, which was favourable for high primary amine selectivity, was the most stable structure on Ru compared with other intermediate structures.

α,β-Unsaturated imines via Ru-catalyzed coupling of allylic alcohols and amines.

Science.gov (United States)

Rigoli, Jared W; Moyer, Sara A; Pearce, Simon D; Schomaker, Jennifer M

2012-03-07

A convenient synthesis of α,β-unsaturated imines requiring only an allylic alcohol, an amine and a Ru catalyst has been developed. The use of large excesses of oxidant and the purification of sensitive intermediates can be avoided.

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.

Electronic bond tuning with heterocyclic carbenes

KAUST Repository

Falivene, Laura

2013-01-01

We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

Vascular Response of Ruthenium Tetraamines in Aortic Ring from Normotensive Rats

Directory of Open Access Journals (Sweden)

Ana Gabriela Conceição-Vertamatti

2015-03-01

Full Text Available Background: Ruthenium (Ru tetraamines are being increasingly used as nitric oxide (NO carriers. In this context, pharmacological studies have become highly relevant to better understand the mechanism of action involved. Objective: To evaluate the vascular response of the tetraamines trans-[RuII(NH34(Py(NO]3+, trans-[RuII(Cl(NO (cyclan](PF62, and trans-[RuII(NH34(4-acPy(NO]3+. Methods: Aortic rings were contracted with noradrenaline (10−6 M. After voltage stabilization, a single concentration (10−6 M of the compounds was added to the assay medium. The responses were recorded during 120 min. Vascular integrity was assessed functionally using acetylcholine at 10−6 M and sodium nitroprusside at 10−6 M as well as by histological examination. Results: Histological analysis confirmed the presence or absence of endothelial cells in those tissues. All tetraamine complexes altered the contractile response induced by norepinephrine, resulting in increased tone followed by relaxation. In rings with endothelium, the inhibition of endothelial NO caused a reduction of the contractile effect caused by pyridine NO. No significant responses were observed in rings with endothelium after treatment with cyclan NO. In contrast, in rings without endothelium, the inhibition of guanylate cyclase significantly reduced the contractile response caused by the pyridine NO and cyclan NO complexes, and both complexes caused a relaxing effect. Conclusion: The results indicate that the vascular effect of the evaluated complexes involved a decrease in the vascular tone induced by norepinephrine (10−6 M at the end of the incubation period in aortic rings with and without endothelium, indicating the slow release of NO from these complexes and suggesting that the ligands promoted chemical stability to the molecule. Moreover, we demonstrated that the association of Ru with NO is more stable when the ligands pyridine and cyclan are used in the formulation of the compound.

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.

New Ru(II)N'NN'-type pincer complexes: synthesis, characterization and the catalytic hydrogenation of CO_2 or bicarbonates to formate salts

International Nuclear Information System (INIS)

Zengjin Dai; Qi Luo; Hengjiang Cong; Jing Zhang; Tianyou Peng

2017-01-01

[RuCl(L1)(MeCN)_2]Cl (1) and [RuCl(L2)(MeCN)_2]Cl (2) complexes were prepared through the reaction of [RuCl2(p-cymene)]_2 with 2,6-bis(benzimidazole-2-yl)-4-hydroxy-pyridine (L1) or 2,6-bis(benzimidazole- 2-yl) pyridine (L2) in acetonitrile, respectively. The treatment of [Ru(OTf)(L2)(MeCN)_2]OTf (3) with 1 equivalent of PPh_3 in ethanol resulted in the formation of [Ru(L2"-"1)(MeCN)(PPh_3)_2]OTf (4), in which one of the N-H moieties of L2 is deprotonated to give an anionic ligand (L2"-"1). It was found that complex 1 can catalyze the hydrogenation of CO_2 to formate salts, producing sodium formate in 34.0% yield with a turnover number (TON) of 407 under the optimized conditions. Further investigations revealed that complexes 1-4 can efficiently catalyze the hydrogenation of sodium bicarbonate to sodium formate, and the catalytic activity follows the order 4 ≥ 1 ≥ 2 ≅ 3. In particular, sodium formate was obtained in good yield (77%) with a high TON (1530) when complex 4 was used as the catalyst. The present results illustrate a new example of Ru(II) complexes bearing a rigid N'NN' framework for the efficient hydrogenation of CO_2 to formate salts in a homogeneous system. (authors)

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

Directory of Open Access Journals (Sweden)

Jesús Antonio Luque-Urrutia

2017-12-01

Full Text Available Density functional theory (DFT calculations have been used to investigate the behavior of different transition metals from Groups 8 (Fe and Ru and 9 (Co and Rh in an already well-known catalytic mechanism, which is based on an Ru(SIMes(PPh3Cl2=CH(Ph complex. As expected, Ru has proven to perform better than their Fe, Co, and Rh counterparts. Even though the topographic steric maps analysis shows no difference in sterical hindrance for any of the metal centers, geometrically, the Fe-based species show a high rigidity with shorter and stronger bonds confirmed by Mayer Bond Orders. The systems bearing Co as a metallic center might present a reactivity that is, surprisingly, too high according to conceptual DFT, which would consequently be a drawback for the formation of the fundamental species of the reaction pathway: the metallacycle intermediate.

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.

Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

Energy Technology Data Exchange (ETDEWEB)

T. Brent Gunnoe

2011-02-17

, which has provided a comprehensive understanding of the impact of steric and electronic parameters of 'L' on the catalytic hydroarylation of olefins. (3) We have completed and published a detailed mechanistic study of stoichiometric aromatic C-H activation by TpRu(L)(NCMe)Ph (L = CO or PMe{sub 3}). These efforts have probed the impact of functionality para to the site of C-H activation for benzene substrates and have allowed us to develop a detailed model of the transition state for the C-H activation process. These results have led us to conclude that the C-H bond cleavage occurs by a {sigma}-bond metathesis process in which the C-H transfer is best viewed as an intramolecular proton transfer. (4) We have completed studies of Ru complexes possessing the N-heterocyclic carbene IMes (IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene). One of these systems is a unique four-coordinate Ru(II) complex that catalyzes the oxidative hydrophenylation of ethylene (in low yields) to produce styrene and ethane (utilizing ethylene as the hydrogen acceptor) as well as the hydrogenation of olefins, aldehydes and ketones. These results provide a map for the preparation of catalysts that are selective for oxidative olefin hydroarylation. (5) The ability of TpRu(PMe{sub 3})(NCMe)R systems to activate sp{sup 3} C-H bonds has been demonstrated including extension to subsequent C-C bond forming steps. These results open the door to the development of catalysts for the functionalization of more inert C-H bonds. (6) We have discovered that Pt(II) complexes supported by simple nitrogen-based ligands serve as catalysts for the hydroarylation of olefins. Given the extensive studies of Pt-based catalytic C-H activation, we believe these results will provide an entry point into an array of possible catalysts for hydrocarbon functionalization.

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)

Ring-shaped functions and Wigner 6j-symbols

International Nuclear Information System (INIS)

Mardoyan, L.G.; Erevanskij Gosudarstvennyj Univ., Erevan

2006-01-01

The explicit expression for the ring-shaped matrix connecting the ring-shaped functions relating to different values of the axial parameter is obtained. The connection of this matrix with Wigner 6j-symbols is found out. The motion of quantum particle in the ring-shaped model with the zero priming potential is investigated. The bases of this model, which are factored in spherical cylindrical coordinates, are obtained. The formula generalizing the Rayleigh expansion of a plane wave with respect to spherical waves in the ring-shaped model is deduced [ru

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...

A new Kaempferol-based Ru(II) coordination complex, Ru(kaem)Cl(DMSO)3: Structure and absorption-emission spectroscopy study

International Nuclear Information System (INIS)

Shao, Ming Wei; Gang, Jong Back; Kim, Sang Ho; Yoon, Min Young

2016-01-01

Recent interest in developing a new anticancer drug with low side effects has led to the study of the combination of two new anticancer drugs. Although both kaempferol (kaem) and Ru-based metal complexes have not been proven as effective drugs, their unique anticancer activities with reduced side effects have drawn our attention to the need for further studies on their potential in anticancer application. Herein, we report the synthesis, characterization, structure, and spectroscopic properties of a kaem-based Ru (II) complex, RuCl(kaem)(DMSO) 3 (1). Because of the presence of a catechol-like functional group in its dihydropyran ring, kaem can strongly bind to the Ru(II) metal center in a basic medium. The molecular structure of the complex was characterized by spectroscopic studies and X-ray crystal structure analysis. In addition, the complex forms a molecular dimer as a result of the cooperative effect of H-bonding and π–π stacking interactions. Moreover, the molecular dimer forms a ladder-like one-dimensional network structure by water mediated H-bonding that further extended into a three-dimensional packing structure. UV–Vis spectroscopy studies of the complex demonstrated the appearance of a strong metal to ligand charge transfer (MLCT) band in the visible region with strong fluorescence emission derived from the MLCT. Further studies are now in progress to demonstrate synergetic anticancer activity

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...

Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media

International Nuclear Information System (INIS)

King, R.B.; Bhattacharyya, N.K.; Wiemers, K.D.

1994-08-01

Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 -, and NO 2 - were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO 2 H → H 2 + CO 2 catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100 degree C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl 3 ·3H 2 O, was found to be the most active catalyst for hydrogen generation from formic acid above ∼80 degree C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen production rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature (∼90 degree C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO 2 and NO/N 2 O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion

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-.

Chlorine Evolution Reaction on RuO2(110): Ab initio Atomistic Thermodynamics Study - Pourbaix Diagrams

International Nuclear Information System (INIS)

Exner, Kai S.; Anton, Josef; Jacob, Timo; Over, Herbert

2014-01-01

Graphical abstract: - Highlights: • Using the method Pourbaix diagram we identified the oxygen covered RuO 2 (110) surface as the catalytically active phase under chlorine evolution reaction (CER) conditions. This active phase is compared with the active phase in the Deacon process, the heterogeneous gas phase counterpart of the CER. - Abstract: Constrained ab initio thermodynamics in the form of a Pourbaix diagram can greatly assist kinetic modeling of a particular electrochemical reaction such as the chlorine evolution reaction (CER) over RuO 2 (110). Pourbaix diagrams reveal stable surface structures, as a function of pH and the potential. The present DFT study indicates that the Pourbaix diagram in the CER potential region above 1.36 V and pH values around zero is dominated by a stable surface structure in which all coordinatively undercoordinated Ru sites (Ru cus ) are capped by on-top oxygen (O ot ). This oxygen saturated RuO 2 (110) surface is considered to serve as the catalytically active phase in the CER, quite in contrast to the heterogeneously catalyzed HCl oxidation (Deacon process), for which the active RuO 2 (110) surface is mainly covered by on-top chlorine. The active sites in the CER are suggested to be Ru cus O ot surface complexes, while in the Deacon process both undercoordinated surface Ru and oxygen sites must be available for the activation of HCl molecules

Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

Science.gov (United States)

Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

2018-04-25

The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

Method of preparing Ru-immobilized polymer-supported catalyst for hydrogen generation from NaBH{sub 4} solution

Energy Technology Data Exchange (ETDEWEB)

Chen, Ching-Wen; Chen, Chuh-Yung; Huang, Yao-Hui [Department of Chemical Engineering, National Cheng Kung University, No.1, University Road, Tainan City 70101 (China)

2009-03-15

A method of preparing a polymer-supported catalyst for hydrogen generation is introduced in this article. This polymer-supported catalyst is the structure of ruthenium (Ru) nanoparticle immobilized on a monodisperse polystyrene (PSt) microsphere. The diameter of the Ru nanoparticle is around 16 nm, and the diameter of the PSt microsphere is 2.65 um. This preparation method is accomplished by two unique techniques: one is sodium lauryl sulfate/sodium formaldehyde sulfoxylate (SLS/SFS) interface-initiated system, the other is 2-methacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester (GMA-IDA) chelating monomer. By taking advantage of these two techniques, Ru{sup 3+} ion will be chelated and then reduced to Ru{sup (0)} nanoparticle over PSt surface predominantly. The hydrolysis of alkaline sodium borohydride (NaBH{sub 4}) solution catalyzed by this Ru-immobilized polymer-supported catalyst is also examined in this article. It reveals that the hydrogen generation rate is 215.9 ml/min g-cat. in a diluted solution containing 1 wt.% NaBH{sub 4} and 1 wt.% NaOH, and this Ru-immobilized polymer-supported catalyst could be recycled during the reaction. (author)

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

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 ...

A new Kaempferol-based Ru(II) coordination complex, Ru(kaem)Cl(DMSO){sub 3}: Structure and absorption-emission spectroscopy study

Energy Technology Data Exchange (ETDEWEB)

Shao, Ming Wei; Gang, Jong Back; Kim, Sang Ho; Yoon, Min Young [Gachon University, Sungnam (Korea, Republic of)

2016-10-15

Recent interest in developing a new anticancer drug with low side effects has led to the study of the combination of two new anticancer drugs. Although both kaempferol (kaem) and Ru-based metal complexes have not been proven as effective drugs, their unique anticancer activities with reduced side effects have drawn our attention to the need for further studies on their potential in anticancer application. Herein, we report the synthesis, characterization, structure, and spectroscopic properties of a kaem-based Ru (II) complex, RuCl(kaem)(DMSO){sub 3} (1). Because of the presence of a catechol-like functional group in its dihydropyran ring, kaem can strongly bind to the Ru(II) metal center in a basic medium. The molecular structure of the complex was characterized by spectroscopic studies and X-ray crystal structure analysis. In addition, the complex forms a molecular dimer as a result of the cooperative effect of H-bonding and π–π stacking interactions. Moreover, the molecular dimer forms a ladder-like one-dimensional network structure by water mediated H-bonding that further extended into a three-dimensional packing structure. UV–Vis spectroscopy studies of the complex demonstrated the appearance of a strong metal to ligand charge transfer (MLCT) band in the visible region with strong fluorescence emission derived from the MLCT. Further studies are now in progress to demonstrate synergetic anticancer activity.

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.

Fingerprint elements scatter analysis on ancient chinese Ru porcelains samples

International Nuclear Information System (INIS)

Gao Zhengyao; Wang Jie; Chen Xiande

1997-01-01

Altogether 28 samples, mainly including glazes and bodies of ancient Chinese Ru porcelain, were analyzed by NAA technique and the contents of 36 elements were compared. The scatter analysis for nine fingerprint-elements indicates that almost all ancient Chinese Ru porcelain samples had nearly identical and long-term stable source of raw materials although they were fired in different kilns, at varying time and with distinct colors, and moreover, the source of raw materials for modern Ru porcelain seems to approach that for ancient one. The close provenance relation between ancient Jun porcelain and ancient Ru porcelain is also preliminarily verified. The glaze material of Jingdezhen white porcelain is totally different from all other samples. It shows that the former came from a separate source

Unravelling The Mechanism of Basic Aqueous Methanol Dehydrogenation Catalyzed By Ru-PNP Pincer Complexes

DEFF Research Database (Denmark)

Alberico, Elisabetta; Lennox, Alastair J. J.; Vogt, Lydia K.

2016-01-01

Ruthenium PNP complex 1a (RuH(CO)Cl(HN(C2H4Pi-Pr2)2)) represents a state-of-the-art catalyst for low-temperature (methanol dehydrogenation to H2 and CO2. Herein, we describe an investigation that combines experiment, spectroscopy, and theory to provide a mechanistic rationale...

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

Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

DEFF Research Database (Denmark)

Sølvhøj, Amanda Birgitte; Madsen, Robert

2011-01-01

The ruthenium complex [RuCl2(IiPr)(p-cymene)] catalyzes the direct condensation of primary alcohols into esters and lactones with the release of hydrogen gas. The reaction is most effective with linear aliphatic alcohols and 1,4-diols and is believed to proceed with a ruthenium dihydride...

Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

DEFF Research Database (Denmark)

Mazziotta, Andrea; Madsen, Robert

2017-01-01

Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

Science.gov (United States)

Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

2014-01-01

Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

Energy Technology Data Exchange (ETDEWEB)

Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

2018-03-06

Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

KAUST Repository

Hou, Duenren

2010-11-01

A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.

Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

KAUST Repository

Hou, Duenren; Kuan, Tingchun; Li, YuKai; Lee, Richmond; Huang, Kuo-Wei

2010-01-01

A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.

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...

Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

Science.gov (United States)

You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

2017-02-03

A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

Preparation of deuterated heterocyclic five-membered ring compounds (furan, thiophene, pyrrole, and derivatives) by base-catalyzed hydrogen isotope exchange with deuterium oxide

International Nuclear Information System (INIS)

Heinrich, K.H.; Herrmann, M.; Moebius, G.; Sprinz, H.

1984-01-01

Several deuterated heterocyclic compounds of the type of furan,thiophene and pyrrole were prepared by base-catalyzed proton exchange with deuterium oxide at temperatures above 423 K in a closed system. The determination of deuterium and its distribution within the molecules was carried out by mass spectrometry and 1 H nmr spectrometry. (author)

Several novel Ru(II) and Ru(III) complexes formed by reduction of (RuO4bipy) and (RuO3phen)2O with hydroquinone and methanol

International Nuclear Information System (INIS)

Ishiyama, Toshio

1975-01-01

The geometrical isomers, cis-dichloro-trans-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II) and cis-dichloro-cis-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II), [RuCl 2 (MeOH)(QH 2 )bipy] (complex I and II), were synthesized by reduction and substitution reactions of [RuO 4 bipy] and [RuO 2 (OH) 2 bipy] with hydroquinone in hydrochloric acid solution, and methanol. cis-Chloro(hydroquinonato)bis(2,2'-bipyridine)ruthenium(II), cis-[RuCl(QH)(bipy) 2 ], was obtained from the substitution reaction of complex I or II with 2,2'-bipyridine in methanol, and cis-chloro(hydroquinone)bis(2,2'-bipyridine)ruthenium(II) chloride, cis-[RuCl(QH 2 )(bipy) 2 ]Cl, was also obtained from the substitution of cis-trans-[RuCl 2 (MeOH)(QH 2 )bipy] in methanol containing hydrochloric acid. cis-Dihydroxobis(2,2'-bipyridine)ruthenium(II), cis-[Ru(OH) 2 (bipy) 2 ], was obtained by heating an aqueous solution of cis-[RuCl(QH)(bipy) 2 ]. Trihydroxoaquo(1,10-phenanthroline)ruthenium(III), [Ru(OH) 3 (H 2 O)phen] was also synthesized from [RuO 3 phen] 2 O and [Ru(OH) 3 phen] 2 O by reduction reactions similar to those used for [RuCl 2 (MeOH)(QH 2 )bipy]. These complexes were characterized by the infrared, visible and ultraviolet absorption spectra, and also by polarographic and magnetic measurements. The structures are discussed. (auth.)

Radiation diagnosis of pelvic ring damages in acute injury

International Nuclear Information System (INIS)

Dytalov, M.M.

2000-01-01

Data on 58 victims with multifocal damages to the pelvic ring were used to examine the diagnostic potentialities of different radiation diagnostic techniques and to compare their resolving power. The later was 65.1, 83.3 and 94.7% in plain and multidimensional X-ray studies, and computed tomography, respectively. Complex of signs is described closed sacral fractures on the plain and oblique pelvic inlet (caudal) radiograms proposed, which could improve the diagnosis of fractures by 8.8 times, and an original orthopedic gauze-plate for the detection and estimation of invisible pelvic bone displacement, and an original procedure for pelvic X-ray study with target load in acute injury. This all can improve the quality of examination of casualties substantially and define indications for different treatments more precise [ru

Novel Electronic Structures of Ru-pnictides RuPn (Pn = P, As, Sb)

Science.gov (United States)

Goto, H.; Toriyama, T.; Konishi, T.; Ohta, Y.

Density-functional-theory-based electronic structure calculations are made to consider the novel electronic states of Ru-pnictides RuP and RuAs where the intriguing phase transitions and superconductivity under doping of Rh have been reported. We find that there appear nearly degenerate flat bands just at the Fermi level in the high-temperature metallic phase of RuP and RuAs; the flat-band states come mainly from the 4dxy orbitals of Ru ions and the Rh doping shifts the Fermi level just above the flat bands. The splitting of the flat bands caused by their electronic instability may then be responsible for the observed phase transition to the nonmagnetic insulating phase at low temperatures. We also find that the band structure calculated for RuSb resembles that of the doped RuP and RuAs, which is consistent with experiment where superconductivity occurs in RuSb without Rh doping.

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.

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.

Study the Polyol Process of Preparing the ru Doped FePt Nanoparticles

Science.gov (United States)

Lee, Chih-Hao; Hsu, Jen-Ho; Su, Hui-Chia; Huang, Tzu Wen

The structure of Ru doped FePt nanoparticles using polyol process was studied. The particle size grown is around 5 nm, and a shell structure might be formed. By selecting the time and temperature of adding the Ru precursors into solution, three different processes to synthesize the FePtRu particles were studied resulting in different growing mechanics. The possible models during the reaction process are also discussed. The phase transition temperature for the as-grown FCC FePt nanoparticle to transform into L10 FePt nanoparticle is about 823 K which is about the same as the one without doping Ru atoms. From the XAS study of each element, the possible scenario is that: although Ru atoms with the size close to the Pt, they do not totally replace the Pt sites in the FePt alloy. Instead, most of Ru formed a shell outside the FePt nanoparticles and Fe atoms are replaced.

Nucleophilic ring opening reactions of aziridines.

Science.gov (United States)

Akhtar, Rabia; Naqvi, Syed Ali Raza; Zahoor, Ameer Fawad; Saleem, Sameera

2018-05-04

Aziridine ring opening reactions have gained tremendous importance in the synthesis of nitrogen containing biologically active molecules. During recent years, a great effort has been put forward by scientists toward unique bond construction methodologies via ring opening of aziridines. In this regard, a wide range of chiral metal- and organo-catalyzed desymmetrization reactions of aziridines have been reported with carbon, sulfur, oxygen, nitrogen, halogen, and other nucleophiles. In this review, an outline of methodologies adopted by a number of scientists during 2013-2017 for aziridine ring opening reactions as well as their synthetic applications is described.

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

Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

Energy Technology Data Exchange (ETDEWEB)

Lewera, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw (Poland); Inukai, J. [Clean Energy Research Center, University of Yamanashi, 7-32 Miyamae-cho, Kofu 400-0006 (Japan); Zhou, W.P. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Cao, D. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Duong, H.T. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Alonso-Vante, N. [Laboratory of Electrocatalysis, UMR-CNRS 6503, University of Poitiers, F-86022 Poitiers (France)]. E-mail: Nicolas.Alonso.Vante@univ-poitiers.fr; Wieckowski, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)]. E-mail: andrzej@scs.uiuc.edu

2007-05-10

Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO{sub 2} or SO {sub x} forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples.

Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

International Nuclear Information System (INIS)

Lewera, A.; Inukai, J.; Zhou, W.P.; Cao, D.; Duong, H.T.; Alonso-Vante, N.; Wieckowski, A.

2007-01-01

Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO 2 or SO x forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples

Synthesis, characterization, DNA binding and catalytic applications of Ru(III) complexes.

Science.gov (United States)

Shoair, A F; El-Shobaky, A R; Azab, E A

2015-01-01

A new series of azodye ligands 5-chloro-3-hydroxy-4-(aryldiazenyl)pyridin-2(1H)-one (HLn) were synthesized by coupling of 5-chloro-3-hydroxypyridin-2(1H)-one with aniline and its p-derivatives. These ligands and their Ru(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl were characterized by elemental analyses, IR, (1)H NMR and UV-Visible spectra as well as magnetic and thermal measurements. The molar conductance measurements proved that all the complexes are electrolytes. IR spectra show that the ligands (HLn) acts as a monobasic bidentate ligand by coordinating via the nitrogen atom of the azo group (NN) and oxygen atom of the deprotonated phenolic OH group, thereby forming a six-membered chelating ring and concomitant formation of an intramolecular hydrogen bond. The molecular and electronic structures of the investigated compounds (HLn) were also studied using quantum chemical calculations. The calf thymus DNA binding activity of the ligands (HLn) and their Ru(III) complexes were studied by absorption spectra and viscosity measurements. The mechanism and the catalytic oxidation of benzyl alcohol by trans-[Ru(Ln)2(AsPh3)2]Cl with hydrogen peroxide as co-oxidant were described. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Ruthenium nanoparticles supported on CeO2 for catalytic permanganate oxidation of butylparaben.

Science.gov (United States)

Zhang, Jing; Sun, Bo; Guan, Xiaohong; Wang, Hui; Bao, Hongliang; Huang, Yuying; Qiao, Junlian; Zhou, Gongming

2013-11-19

This study developed a heterogeneous catalytic permanganate oxidation system with ceria supported ruthenium, Ru/CeO2 (0.8‰ as Ru), as catalyst for the first time. The catalytic performance of Ru/CeO2 toward butylparaben (BP) oxidation by permanganate was strongly dependent on its dosage, pH, permanganate concentration and temperature. The presence of 1.0 g L(-1) Ru/CeO2 increased the oxidation rate of BP by permanganate at pH 4.0-8.0 by 3-96 times. The increase in Ru/CeO2 dosage led to a progressive enhancement in the oxidation rate of BP by permanganate at neutral pH. The XANES analysis revealed that (1) Ru was deposited on the surface of CeO2 as Ru(III); (2) Ru(III) was oxidized by permanganate to its higher oxidation state Ru(VI) and Ru(VII), which acted as the co-oxidants in BP oxidation; (3) Ru(VI) and Ru(VII) were reduced by BP to its initial state of Ru(III). Therefore, Ru/CeO2 acted as an electron shuttle in catalytic permanganate oxidation process. LC-MS/MS analysis implied that BP was initially attacked by permanganate or Ru(VI) and Ru(VII) at the aromatic ring, leading to the formation of various hydroxyl-substituted and ring-opening products. Ru/CeO2 could maintain its catalytic activity during the six successive runs. In conclusion, catalyzing permanganate oxidation with Ru/CeO2 is a promising technology for degrading phenolic pollutants in water treatment.

Synthesis of pyrrolo(2,3-b)quinolines by palladium-catalyzed heteroannulation

International Nuclear Information System (INIS)

Gee, Moon Bae; Lee, Won Jung; Yum, Eul Kgun

2003-01-01

Palladium-catalyzed heteroannulation of 2-amino-3-iodoquinoline derivatives and 1-trimethylsilyl internal alkynes provided highly regioselective pyrrolo(2,3-b)quinolines with trimethylsilyl group next to the nitrogen atom in the pyrrole ring

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

Group program procedure for machining seal rings of steam turbines on digital computer controlled machines

International Nuclear Information System (INIS)

Glukhikh, V.K.; Skvortsov, S.B.; Sidorov, V.A.

1982-01-01

Developed is a group program procedure for turning machining of seal rings, including the use of new progressive high-accuracy equipment, universal device for securing of all nomenclature of treated seal rings, necessary cutting tools and program control of the process of treatment. Introduction of a new technological process permitted to improve the quality of treated seal rings; to reduce the labour consumption in 30...40% [ru

Preparation and characterization of PtRu/C, PtBi/C, PtRuBi/C electrocatalysts for direct electro-oxidation of ethanol in PEM fuels cells using the method of reduction by sodium borohydride

International Nuclear Information System (INIS)

Brandalise, Michele

2010-01-01

Pt/C, PtBi/C, PtRu/C and PtRuBi/C electrocatalysts were prepared by a borohydride reduction methodology and tested for ethanol oxidation. This methodology consists in mix a solution with sodium hydroxide and sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. It was studied the addition method of borohydride (drop by drop addition or rapid addition). The obtained electrocatalysts were characterized by energy dispersive X ray spectroscopy (EDX), thermogravimetric analysis (TGA), X ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry. The ethanol electro-oxidation was studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. The electrocatalysts were tested in real conditions of operation by unit cell tests. The stability of PtRuBi/C electrocatalysts was evaluated by cyclic voltammetry, chronoamperometry using the ultra-thin porous coating technique and ring-disk electrode. The PtRuBi/C electro catalyst apparently presented a good performance for ethanol electro-oxidation but experimental evidences showed accentuated bismuth dissolution. (author)

Carbon supported nanoparticles Pt Ru (Pt Ru/C electrocatalysts) prepared using electron beam irradiation; Preparacao de nanoparticulas de PtRu suportadas em carbono (eletrocatalisadores PtRu/C) utilizando feixe de eletrons

Energy Technology Data Exchange (ETDEWEB)

Silva, Dionisio F. da; Oliveira Neto, Almir; Pino, Eddy S.; Linardi, Marcelo; Spinace, Estevam V. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Programa de Celulas a Combustivel], e-mail: espinace@ipen.br, e-mail: dfsilva@ipen.br

2006-07-01

Carbon-supported Pt Ru (electrocatalysts PtRu/C nanoparticles) were prepared submitting a water/ethylene glycol mixture containing Pt(IV) and Ru(III) ions and the carbon support to electron beam irradiation. The PtRu/C electrocatalysts were characterized by EDX, XRD and cyclic voltammetry and tested for methanol electro-oxidation aiming fuel cell application. The obtained PtRu/C electrocatalysts were more active for methanol electro-oxidation than the commercial PtRu/C ETEK electrocatalyst at ambient temperature. (author)

Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

Science.gov (United States)

Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

2014-06-16

Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The fingerprint elements analysis on the provenance relation between ancient chinese Ru porcelain and Jun porcelain

International Nuclear Information System (INIS)

Zhao Weijuan; Xie Jianzhong; Li Guoxia; Gao Zhengyao; Li Rongwu; Zhang Bin; Feng Songlin; Huang Zhongxiang; Jia Xiuqin; Han Song

2002-01-01

The 46 samples of glazes and bodies of the ancient Chinese Ru porcelain, Jun Porcelain and imitative porcelain were analyzed by neutron activation analysis (NAA). The contents of 36 elements for each sample were measured, the eight elements were chosen as the fingerprint elements to complete scatter analysis. The result showed that the ancient Chinese Ru porcelain and Jun porcelain had almost identical and stable sources of raw materials. The close provenance relation between ancient Chinese Ru porcelain and Jun porcelain was preliminarily verified. It is found that most modern Jun porcelain samples were similar to the ancient Chinese Jun porcelain, three modern Ru porcelain samples were similar to the ancient Chinese Ru porcelain. Jingdezhen porcelain has no relation to Ru porcelain and Jun porcelain

High current vacuum closing switch

International Nuclear Information System (INIS)

Dolgachev, G.I.; Maslennikov, D.D.; Romanov, A.S.; Ushakov, A.G.

2005-01-01

The paper proposes a powerful pulsed closing vacuum switch for high current commutation consisting of series of the vacuum diodes with near 1 mm gaps having closing time determined by the gaps shortening with the near-electrode plasmas [ru

Investigation of the ROMP catalysis mechanism of norbornene using methods of density functional; Investigacao do mecanismo de catalise ROMP do norborneno utilizando metodos de funcional de densidade

Energy Technology Data Exchange (ETDEWEB)

Silva, Carlos Pereira da, E-mail: carlosps1985@gmail.co [Institutor Federal de Educacao, Ciencia e Tecnologia do Piaui, Teresina, PI (Brazil); Lima, Francisco das Chagas Alves [Universidade Estadual do Piaui, Teresina, PI (Brazil). Coordenacao de Quimica; Leal, Regis Casimiro; Moita Neto, Jose Machado [Universidade Federal do Piaui (UFPI), Teresina, PI (Brazil)

2010-07-01

This work presents a density functional theory study of the norbornene ROMP metathesis reactions. The energies have been calculated in a Grubbs catalyst model Cl{sub 2}(PH{sub 3}){sub 2}Ru=CH{sub 2}. The geometries and energy profile are similar to the Grubbs methylidene (Cl{sub 2}(PCy{sub 3}){sub 2}Ru=CH{sub 2} real model. It was found that the metathesis reaction proceeds via associative mechanism (catalyst-norbornene) followed by dissociative substitution of a phosphine ligand with norbornene, giving a monophosphine complex. The results are in reasonable agreement with the available experimental data. The dissociation energy of the phosphines is predicted to be 23.2 kcal mol{sup -1}. (author)

101Ru NQR study in superconducting CeRu2

International Nuclear Information System (INIS)

Matsuda, Kazuyuki; Kohori, Yoh; Kohara, Takao

1995-01-01

We present measurements of the NQR spectrum and the nuclear spin lattice relaxation rate, 1/T 1 , of 101 Ru in superconducting CeRu 2 from 1.9 K to 10 K. From the NQR spectrum, the electric quadrupole interaction parameters were determined to be ν Q =13.2 MHz and η=0.1/T 1 varies in proportion to temperature in the normal state, and has the Hebel-Slichter coherence peak just below the superconducting transition temperature, T C , of 6.2 K, and decreases exponentially at low temperatures with the energy gap of 2Δ=4.0k B T C . 101 Ru NQR study indicates that CeRu 2 is an s-wave and strong-coupling superconductor. (author)

Synthesis and magnetic properties of carbon-coated FeRu, CoRu, and NiRu nanoalloys

Energy Technology Data Exchange (ETDEWEB)

El-Gendy, A.A.; Khavrus, V.O.; Hampel, S.; Leonhardt, A.; Klingeler, R.; Buechner, B. [Leibniz Institute for Solid State and Materials Research (IFW) Dresden (Germany)

2010-07-01

Carbon coated FeRu, CoRu and NiRu nanoalloys have been synthesised by high pressure chemical vapour deposition (HPCVD). The formation of the core-shell nanoalloys with a mean diameter around 8 nm has been confirmed by means of high resolution transmission electron microscopy imaging (HRTEM), energy dispersive X-ray (EDX) analysis, and X-ray diffraction (XRD). We show the effect of the synthesis parameters on the actual composition of the nanoalloys and on their magnetic properties and we discuss their feasibility for applications in medical hyperthermia.

The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: nicolas.alonso.vante@univ-poitiers.f [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)

2010-11-01

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

Science.gov (United States)

Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

2014-12-01

Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

Metalloradical Reactivity of RuI and Ru0 Stabilized by an Indole-Based Tripodal Tetraphosphine Ligand

NARCIS (Netherlands)

van de Watering, F.F.; van der Vlugt, J.I.; Dzik, W.I.; de Bruin, B.; Reek, J.N.H.

2017-01-01

The tripodal, tetradentate tris(1-(diphenylphosphanyl)-3-methyl-1H-indol-2-yl)phosphane PP3-ligand 1 stabilizes Ru in the RuII, RuI, and Ru0 oxidation states. The octahedral [(PP3)RuII(Cl)2] ( 2 ), distorted trigonal bipyramidal [(PP3)RuI(Cl)] ( 3 ), and trigonal bipyramidal [(PP3)Ru0(N2)] ( 4 )

Magnetic properties of Heusler alloy Mn2RuGe and Mn2RuGa ribbons

International Nuclear Information System (INIS)

Yang, Ling; Liu, Bohua; Meng, Fanbin; Liu, Heyan; Luo, Hongzhi; Liu, Enke; Wang, Wenhong; Wu, Guangheng

2015-01-01

Heusler alloys Mn 2 RuGe and Mn 2 RuGa have been prepared by melt-spinning method successfully. Theoretical and experimental studies reveal a ferrimagnetic ground state in the two alloys. The Curie temperatures are 303 K for Mn 2 RuGe and 272 K for Mn 2 RuGa. The calculated total spin moments of Mn 2 RuGe and Mn 2 RuGa are integral values of 2.00 μ B and 1.03 μ B , respectively. And the theoretical spin polarization ratio is also quite high. However, due to the atomic disorder in the ribbons, the saturation moments of them measured at 5 K are smaller than the calculated values, especially that of Mn 2 RuGa. This coincides with the disappearance of the superlattice reflection (111) and (200) peaks in the XRD pattern of Mn 2 RuGa. Annealing Mn 2 RuGa ribbon at 773 K can enhance the atomic ordering. Both saturation magnetic moment and Curie temperature increase obviously after the heat treatment. - Highlights: • Mn 2 RuGe and Mn 2 RuGa have been prepared by melt-spinning successfully. • Ferrimagnetic ground state has been confirmed in Mn 2 RuGe and Mn 2 RuGa. • High spin polarization has been predicted in Mn 2 RuGe. • Melt-spinning can be a possible way to adjust the atomic order of Heusler alloys

Shape and catalytic mechanism of RuO{sub 2} particles at CO oxidation reaction conditions. First-principles based multi-scale modeling

Energy Technology Data Exchange (ETDEWEB)

Reuter, Karsten [TU Muenchen (Germany). Lehrstuhl fuer Theoretische Chemie

2016-11-01

For model catalyst studies on low-index single-crystal surfaces close agreement between detailed measurements and quantitative microkinetic modeling can increasingly be achieved. However, for 'real' catalyst particles, such structure-morphology-activity relationships are only scarcely established. This is prototypically reflected by the situation for RuO{sub 2}, as a most active catalyst for CO oxidation. Here, existing first-principles kinetic modeling is restricted to just one facet, namely the RuO{sub 2}(110) surface, which is not able to fully account for activity data obtained from polycrystalline RuO{sub 2} powder catalysts. The overarching objective of this project was correspondingly to close this gap and demonstrate that similarly close agreement as for individual single-crystal model catalysts can also be achieved for catalyst particles. Specifically, we addressed experiments where an intact RuO{sub 2} bulk structure is conserved, and establish the atomic-scale structure and reactivity of other RuO{sub 2} low-index facets under the gas-phase conditions characteristic for catalytic CO oxidation.

Caffeine-catalyzed gels.

Science.gov (United States)

DiCiccio, Angela M; Lee, Young-Ah Lucy; Glettig, Dean L; Walton, Elizabeth S E; de la Serna, Eva L; Montgomery, Veronica A; Grant, Tyler M; Langer, Robert; Traverso, Giovanni

2018-07-01

Covalently cross-linked gels are utilized in a broad range of biomedical applications though their synthesis often compromises easy implementation. Cross-linking reactions commonly utilize catalysts or conditions that can damage biologics and sensitive compounds, producing materials that require extensive post processing to achieve acceptable biocompatibility. As an alternative, we report a batch synthesis platform to produce covalently cross-linked materials appropriate for direct biomedical application enabled by green chemistry and commonly available food grade ingredients. Using caffeine, a mild base, to catalyze anhydrous carboxylate ring-opening of diglycidyl-ether functionalized monomers with citric acid as a tri-functional crosslinking agent we introduce a novel poly(ester-ether) gel synthesis platform. We demonstrate that biocompatible Caffeine Catalyzed Gels (CCGs) exhibit dynamic physical, chemical, and mechanical properties, which can be tailored in shape, surface texture, solvent response, cargo release, shear and tensile strength, among other potential attributes. The demonstrated versatility, low cost and facile synthesis of these CCGs renders them appropriate for a broad range of customized engineering applications including drug delivery constructs, tissue engineering scaffolds, and medical devices. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

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, ...

Theoretical Interpretation of the Ionic Liquid Phase Role in the (R)-Ru-BINAP Catalyzed Hydrogenation of Methylacetoacetate

Czech Academy of Sciences Publication Activity Database

Dytrych, Pavel; Klusoň, Petr; Slater, M.; Šolcová, Olga

2014-01-01

Roč. 111, č. 2 (2014), s. 475-487 ISSN 1878-5190 R&D Projects: GA MPO FR-TI3/057 Institutional support: RVO:67985858 Keywords : Ionic liquid s * chiral catalysis * Ru-BINAP complex Subject RIV: CC - Organic Chemistry Impact factor: 1.170, year: 2014

A new and general method for the preparation of novel II-heterocyclic derivatives of ruthenium [C5Me5Ru (η6-arene)]X (arene = benzene, thiophene, 3-methylthiophene, benzothiophene, pyridine, 2.6 and 3.5-lutidine, quinoline, acridine). X-ray crystal structure of [(C5Me5)2Ru2Cl2(pyridine)2] PF6

International Nuclear Information System (INIS)

Chaudret, B.; Jalon, F.; Perez-Manrique, M.; Lahoz, F.; Plou, F.J.

1990-01-01

Zinc reduction of (Cp*RuCl 2 ) n (Cp* = C 5 Me 5 ) in acetone or THF followed by addition of 1 equivalent of an arene or aromatic heterocycle leads to compounds of general formulation [Cp* Ru(arene)]X (X = Cl, BF 4 ). Coordination of benzene is rapid and competes successfully with any other arene. Thiophene and 3-methylthiophene give stable π adducts whereas benzothiophene is coordinated through the benzene not through the heterocyclic ring. 2.6 and 3.5-lutidine coordinate through the ring, thus demonstrating an electronic rather than steric stabilization. Again, quinoline and acridine coordinate through the benzene ring. Pyridine gives an unstable π adduct in THF. A paramagnetic mixed-valence species, byproduct of the reaction in THF, has been characterized by an X-ray crystal structure determination. Crystals are triclinic, space group P-1

Conversion of cellulose and cellobiose into sorbitol catalyzed by ruthenium supported on a polyoxometalate/metal-organic framework hybrid.

Science.gov (United States)

Chen, Jinzhu; Wang, Shengpei; Huang, Jing; Chen, Limin; Ma, Longlong; Huang, Xing

2013-08-01

Cellulose and cellobiose were selectively converted into sorbitol over water-tolerant phosphotungstic acid (PTA)/metal- organic-framework-hybrid-supported ruthenium catalysts, Ru-PTA/MIL-100(Cr), under aqueous hydrogenation conditions. The goal was to investigate the relationship between the acid/metal balance of bifunctional catalysts Ru-PTA/MIL-100(Cr) and their performance in the catalytic conversion of cellulose and cellobiose into sugar alcohols. The control of the amount and strength of acid sites in the supported PTA/MIL-100(Cr) was achieved through the effective control of encapsulated-PTA loading in MIL-100(Cr). This design and preparation method led to an appropriately balanced Ru-PTA/MIL-100(Cr) in terms of Ru dispersion and hydrogenation capacity on the one hand, and acid site density of PTA/MIL-100(Cr) (responsible for acid-catalyzed hydrolysis) on the other hand. The ratio of acid site density to the number of Ru surface atoms (nA /nRu ) of Ru-PTA/MIL-100(Cr) was used to monitor the balance between hydrogenation and hydrolysis functions; the optimum balance between the two catalytic functions, that is, 8.84sorbitol of 57.9% at complete conversion of cellulose, and 97.1% yield in hexitols with a selectivity for sorbitol of 95.1% at complete conversion of cellobiose) were obtained using a Ru-PTA/MIL-100(Cr) catalyst with loadings of 3.2 wt % for Ru and 16.7 wt % for PTA. This research thus opens new perspectives for the rational design of acid/metal bifunctional catalysts for biomass conversion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Syntheses, structures, and physicochemical properties of diruthenium compounds of tetrachlorocatecholate with metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) cores (R = CH(3) and C(2)H(5)).

Science.gov (United States)

Miyasaka, H; Chang, H C; Mochizuki, K; Kitagawa, S

2001-07-02

Metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) (R = CH(3) and CH(3)CH(2)) compounds with tetrachlorocatecholate (Cl(4)Cat) have been synthesized in the corresponding alcohol, MeOH and EtOH, from a nonbridged Ru(2+)-Ru(3+) compound, Na(3)[Ru(2)(Cl(4)Cat)(4)(THF)].3H(2)O.7THF (1). In alcohol solvents, compound 1 is continuously oxidized by oxygen to form Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) species. The presence of a characteristic countercation leads to selective isolation of either Ru(3+)(mu-OR)(2)Ru(3+) or Ru(3.5+)(mu-OR)(2)Ru(3.5+) as a stable adduct species. In methanol, Ph(4)PCl and dibenzo-18-crown-6-ether afford Ru(3+)(mu-OMe)(2)Ru(3+) species, [A](2)[Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] ([A](+) = Ph(4)P(+) (2), [Na(dibenzo-18-crown-6)(H(2)O)(MeOH)](+) (3)), while benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(2)][Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] (4). The air oxidation of 1 in a MeOH/EtOH mixed solvent (1:1 v/v) containing benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(H(2)O)][Ru(2)(Cl(4)Cat)(2)(mu-OMe)(2)Na(2)(EtOH)(2)(H(2)O)(2)(MeOH)(2)].(benzo-15-crown-5) (5). Similarly, the oxidation of 1 in ethanol with Ph(4)PCl provides a Ru(3.5+)(mu-OEt)(2)Ru(3.5+) species, (Ph(4)P)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(6)] (7). A selective formation of a Ru(3+)(mu-OEt)(2)Ru(3+) species, (Ph(4)P)(2)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(2)(H(2)O)(2)] (6), is found in the presence of pyrazine or 2,5-dimethylpyrazine. The crystal structures of these compounds, except 2 and 7, have been determined by X-ray crystallography, and all compounds have been characterized by several spectroscopic and magnetic investigations. The longer Ru-Ru bonds are found in the Ru(3+)(mu-OR)(2)Ru(3+) species (2.606(1) and 2.628(2) A for 3 and 6, respectively) compared with those of Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species (2.5260(6) A and 2

ATRP and ROMP: Modular chemical tools for advanced macromolecular engineering

Energy Technology Data Exchange (ETDEWEB)

Morandi, G.; Pioge, S.; Pascual, S.; Montembault, V.; Legoupy, S. [LCOM - Chimie des Polymeres, UCO2M, UMR CNRS 6011, Universite du Maine, Avenue O. Messiaen, 72085 Le Mans (France); Fontaine, L. [LCOM - Chimie des Polymeres, UCO2M, UMR CNRS 6011, Universite du Maine, Avenue O. Messiaen, 72085 Le Mans (France)], E-mail: laurent.fontaine@univ-lemans.fr

2009-03-01

Well-defined graft copolymers were synthesized through the combination of two highly controlled polymerizations, ATRP (Atom Transfer Radical Polymerization) and ROMP (Ring-Opening Metathesis Polymerization). Synthesis of {alpha}-cyclobutenyl polystyrene-b-poly(tert-butyl acrylate) macromonomers was first performed by ATRP from an original initiator. ROMP of these macromonomers using Grubb's generation II catalyst ((IMesH{sub 2})(Cy{sub 3}P)RuCl{sub 2}(CHPh)) has allowed to synthesize well-defined graft copolymers with a polybutadiene backbone and polystyrene-b-poly(tert-butylacrylate) grafts. {alpha}-Cyclobutenyl polystyrene-b-poly(acrylic acid) macromonomers were prepared by acidolysis. An amphiphilic water-soluble {alpha}-cyclobutenyl polystyrene-b-poly(acrylic acid) macromonomer has been successfully employed as stabilizer in emulsion polymerization of styrene.

103Ru for tumor scanning, 2

International Nuclear Information System (INIS)

Mizukawa, Kiichiro

1979-01-01

The mechanism of 103 Ru-uptake in tumors was investigated through the incubation of rat ascites hepatoma cells (AH-130) in vitro with various concentrations of Ru-chloride containing 103 Ru-chloride as a tracer. Quantitative analysis of Ru binding to the cells indicated that ascites hepatoma cells contained high- and low-affinity binding sites for Ru. When ascites hepatoma cells were incubated with Ru after incubation with a low concentration of papain, most of the Ru was not bound to the cells but was found in the medium containing solubilized glycoproteins. However Ru bound mainly to washed cells after the incubation with papain. About 65% of the Ru bound to ascites hepatoma cells was liberated by the papain treatment, and about 45% of the liberated Ru was precipitated by cetyltrimethylammonium bromide, indicating that Ru bound tightly to glycopeptides. These results suggest that the tumor affinity of 103 Ru is related to specific binding to glycopeptides on the tumor cell surface. (author)

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

Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II complexes

Directory of Open Access Journals (Sweden)

Amaresh Mishra

2013-05-01

Full Text Available Pd-catalyzed Sonogashira cross-coupling reactions were used to synthesize novel π-conjugated oligothienylene-ethynylene dendrons and their corresponding terpyridine-based ligands. Their complexation with Ru(II led to interesting novel metallodendrimers with rich spectroscopic properties. All new compounds were fully characterized by 1H and 13C NMR, as well as MALDI–TOF mass spectra. Density functional theory (DFT calculations performed on these complexes gave more insight into the molecular orbital distributions. Photophysical and electrochemical studies were carried out in order to elucidate structure–property relationships and the effect of the dendritic structure on the metal complexes. Photophysical studies of the complexes revealed broad absorption spectra covering from 250 to 600 nm and high molar extinction coefficients. The MLCT emission of these complexes were significantly red-shifted (up to 115 nm compared to the parent [Ru(tpy2]2+ complex.

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.

Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters

Directory of Open Access Journals (Sweden)

Momoko Watanabe

2011-06-01

Full Text Available A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(arylmethanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM achieved excellent enantioselectivities.

A Palladium-Catalyzed Vinylcyclopropane (3 + 2) Cycloaddition Approach to the Melodinus Alkaloids

KAUST Repository

Goldberg, Alexander F. G.

2011-08-19

A palladium-catalyzed (3+2) cycloaddition of a vinylcyclopropane and a β-nitrostyrene is employed to rapidly assemble the cyclopentane core of the Melodinus alkaloids. The ABCD ring system of the natural product family is prepared in six steps from commercially available materials.

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...

Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

Science.gov (United States)

Song, Hai-Jie; Deng, Jin; Cui, Min-Shu; Li, Xing-Long; Liu, Xin-Xin; Zhu, Rui; Wu, Wei-Peng; Fu, Yao

2015-12-21

Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of combinatorial biocatalysis for a unique ring expansion of dihydroxymethylzearalenone.

Science.gov (United States)

Rich, Joseph O; Budde, Cheryl L; McConeghey, Luke D; Cotterill, Ian C; Mozhaev, Vadim V; Singh, Sheo B; Goetz, Michael A; Zhao, Annie; Michels, Peter C; Khmelnitsky, Yuri L

2009-06-01

Combinatorial biocatalysis was applied to generate a diverse set of dihydroxymethylzearalenone analogs with modified ring structure. In one representative chemoenzymatic reaction sequence, dihydroxymethylzearalenone was first subjected to a unique enzyme-catalyzed oxidative ring opening reaction that creates two new carboxylic groups on the molecule. These groups served as reaction sites for further derivatization involving biocatalytic ring closure reactions with structurally diverse bifunctional reagents, including different diols and diamines. As a result, a library of cyclic bislactones and bislactams was created, with modified ring structures covering chemical space and structure activity relationships unattainable by conventional synthetic means.

Preparation and characterization of Pt/C and Pt-Ru/C electrocatalysts for direct ethanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Liu, Zhaolin; Ling, Xing Yi; Su, Xiaodi; Lee, Jim Yang; Gan, Leong Ming [Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602 (Singapore)

2005-09-26

Nano-sized Pt and Pt-Ru colloids are prepared by a microwave-assisted polyol process, and transferred to a toluene solution of decanthiol. Vulcan XC-72 is then added to the toluene solution to adsorb the thiolated Pt and Pt-Ru colloids. Transmission electron microscopy examinations show nearly spherical particles and narrow size distributions for both supported and unsupported metals. The carbon-supported Pt and Pt-Ru nanoparticles are activated by thermal treatment to remove the thiol stabilizing shell. All Pt and Pt-Ru catalysts (except Pt{sub 23}-Ru{sub 77}) give the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure, whereas the Pt{sub 23}-Ru{sub 77} alloy is more typical of the hexagonal close packed (hcp) structure. The electro-oxidation of liquid ethanol on these catalysts is investigated at room temperature by cyclic voltammetry. The results demonstrate that the alloy catalyst is catalytically more active than pure platinum. Preliminary tests on a single cell of a direct ethanol fuel cell (DEFC) indicate that a Pt{sub 52}-Ru{sub 48}/C anode catalyst gives the best electrocatalytic performance among all the carbon-supported Pt and Pt-Ru catalysts. (author)

Substituent-directed structural and physicochemical controls of diruthenium catecholate complexes with ligand-unsupported Ru-Ru bonds.

Science.gov (United States)

Chang, Ho-Chol; Mochizuki, Katsunori; Kitagawa, Susumu

2005-05-30

A family of diruthenium complexes with ligand-unsupported Ru-Ru bonds has been systematically synthesized, and their crystal structures and physical properties have been examined. A simple, useful reaction between Ru2(OAc)4Cl (OAc- = acetate) and catechol derivatives in the presence of bases afforded a variety of diruthenium complexes, generally formulated as [Na(n){Ru2(R4Cat)4}] (n = 2 or 3; R4 = -F4, -Cl4, -Br4, -H4, -3,5-di-t-Bu, and -3,6-di-t-Bu; Cat(2-) = catecholate). The most characteristic feature of the complexes is the formation of short ligand-unsupported Ru-Ru bonds (2.140-2.273 A). These comprehensive studies were carried out to evaluate the effects of the oxidation states and the substituents governing the molecular structures and physicochemical properties. The Ru-Ru bond distances, rotational conformations, and bending structures of the complexes were successfully varied. The results presented in this manuscript clearly demonstrate that the complexes with ligand-unsupported Ru-Ru bonds can sensitively respond to redox reactions and ligand substituents on the basis of the greater degree of freedom in their molecular structures.

Saturn Rings Origin: Quantum Trapping of Superconducting Iced Particles and Meissner Effect Lead to the Stable Rings System

Science.gov (United States)

Viktorovich Tchernyi, Vladimir

2018-06-01

Saturn Rings Origin: Quantum Trapping of Superconducting Iced Particles and Meissner Effect Lead to the Stable Rings System Vladimir V. Tchernyi (Cherny), Andrew Yu. Pospelov Modern Science Institute, SAIBR, Moscow, Russia. E-mail: chernyv@bk.ruAbstractIt is demonstrated how superconducting iced particles of the protoplanetary cloud of Saturn are coming to magnetic equator plane and create the stable enough rings disk. There are two steps. First, after appearance of the Saturn magnetic field due to Meissner phenomenon all particles orbits are moving to the magnetic equator plane. Finally they become distributed as rings and gaps like iron particles around magnet on laboratory table. And they are separated from each other by the magnetic field expelled from them. It takes up to few tens of thousands years with ten meters rings disk thickness. Second, due to their quantum trapping all particles become to be trapped within magnetic well at the magnetic equator plane due to Abrikosov vortex for superconductor. It works even when particles have small fraction of superconductor. During the rings evolution some contribution to the disk also could come from the collision-generated debris of the current moon and from the geysers like it happened due to magnetic coupling of Saturn and Enceladus. The rings are relict of the early days of the magnetic field of Saturn system.

Electrodeposition of Pt-Ru nanoparticles on fibrous carbon substrates in the presence of nonionic surfactant: Application for methanol oxidation

International Nuclear Information System (INIS)

Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W.

2006-01-01

Liquid crystalline and micellar aqueous solutions of the nonionic surfactant Triton X-100 were used to direct the electrodeposition of Pt-Ru nanoparticles onto graphite felts, which were investigated as novel anodes for the direct methanol fuel cell. The effects of surfactant concentration, current density and deposition time in the preparation of these three-dimensional electrodes were studied in a factorial experiment and the electrodes were characterized by SEM and ICP-AES. Cyclic voltammetry, chronoamperometry and chronopotentiometry were carried out to assess the activity of the catalyzed felts for methanol oxidation. The presence of Triton X-100 (40-60 wt.%) coupled with an acidic plating solution were essential for the efficient co-electrodeposition of Ru in the presence of Pt to yield approximately a 1:1 Pt:Ru atomic ratio in the deposit. The highest mass specific activity, 24 A g -1 at 298 K (determined by chronoamperometry after 180 s at 0 V versus Hg/Hg 2 SO 4 , K 2 SO 4std ), was obtained for the Pt-Ru electrodeposited in the presence of 40 wt.% Triton X-100 at 60 A m -2 , 298 K for 90 min. Surfactant mediated electrodeposition is a promising method for meso-scale (ca. 10-60 nm diameter) catalyst particle preparation on three-dimensional electrodes

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.

Inner-shell photodetachment from Ru-

International Nuclear Information System (INIS)

Dumitriu, I.; Gorczyca, T. W.; Berrah, N.; Bilodeau, R. C.; Pesic, Z. D.; Rolles, D.; Walter, C. W.; Gibson, N. D.

2010-01-01

Inner-shell photodetachment from Ru - was studied near and above the 4p excitation region, 29-to-91-eV photon energy range, using a merged ion-photon-beam technique. The absolute photodetachment cross sections of Ru - ([Kr]4d 7 5s 2 ) leading to Ru + , Ru 2+ , and Ru 3+ ion production were measured. In the near-threshold region, a Wigner s-wave law, including estimated postcollision interaction effects, locates the 4p 3/2 detachment threshold between 40.10 and 40.27 eV. Additionally, the Ru 2+ product spectrum provides evidence for simultaneous two-electron photodetachment (likely to the Ru + 4p 5 4d 6 5s 2 state) located near 49 eV. Resonance effects are observed due to interference between transitions of the 4p electrons to the quasibound 4p 5 4d 8 5s 2 states and the 4d→εf continuum. Despite the large number of possible terms resulting from the Ru - 4d open shell, the cross section obtained from a 51-state LS-coupled R-matrix calculation agrees qualitatively well with the experimental data.

Effects of interfacial alignments on the stability of graphene on Ru(0001) substrate

Energy Technology Data Exchange (ETDEWEB)

Gao, Lei; Liu, Yanmin; Ma, Tianbao, E-mail: mtb@mail.tsinghua.edu.cn; Shi, Ruoyu; Hu, Yuanzhong; Luo, Jianbin, E-mail: luojb@mail.tsinghua.edu.cn [State Key Laboratory of Tribology, Tsinghua University, Beijing 100084 (China)

2016-06-27

Structure and electronic properties of two-dimensional materials could be tuned by interfacial misfit or orientation angles. However, graphene grown on Ru(0001) substrate usually shows stable moiré superlattice with a periodicity of 3.0 nm indicating an aligned geometry. The reason for the absence of misaligned structure is still unknown. We have performed first-principles calculation to investigate the microstructure and morphology of graphene on Ru(0001) substrate in both aligned and misaligned geometries with rotation angles of 0°, 7.6°, and 23.4°, respectively. Our results indicate that both the graphene corrugation and moiré superlattice periodicity decrease as the rotation angle increases. Meanwhile the interaction energy between graphene and Ru(0001) substrate also becomes weakened with the rotation angle, as the decrease and discretization of intense charge transfer sites at the graphene/Ru interface, which is closely related to the interface stacking structure. Counterintuitively, the strain energy in graphene also increases anomalously with the rotation angle, which is attributed to the highly distorted local deformation of graphene due to the strong but discrete covalent bonding with Ru substrate. The simultaneous increase in both the interaction energy and strain energy in graphene/Ru(0001) heterostructure with rotation angle contributes to the preferred configuration in the aligned state.

Sol-Gel Process for Making Pt-Ru Fuel-Cell Catalysts

Science.gov (United States)

Narayanan, Sekharipuram; Valdez, Thomas; Kumta, Prashant; Kim, Y.

2005-01-01

final product in a controlled-atmosphere heat treatment. Desirably, the final product is a phase-pure (Pt phase only) Pt-Ru powder with a high specific surface area. The conditions of the controlled- atmosphere heat are critical for obtaining the aforementioned desired properties. A typical heat treatment that yields best results for a catalytic alloy of equimolar amounts of Pt and Ru consists of at least two cycles of heating to a temperature of 300 C and holding at 300 C for several hours, all carried out in an atmosphere of 1 percent O2 and 99 percent N2. The resulting powder consists of crystallites with typical linear dimensions of <10 nm. Tests have shown that the powder is highly effective in catalyzing the electro-oxidation of methanol.

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.

Large-scale ruthenium- and enzyme-catalyzed dynamic kinetic resolution of (rac-1-phenylethanol

Directory of Open Access Journals (Sweden)

Bäckvall Jan-E

2007-12-01

Full Text Available Abstract The scale-up of the ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR of (rac-1-phenylethanol (2 is addressed. The immobilized lipase Candida antarctica lipase B (CALB was employed for the resolution, which shows high enantioselectivity in the transesterification. The ruthenium catalyst used, (η 5-C5Ph5RuCl(CO2 1, was shown to possess very high reactivity in the "in situ" redox racemization of 1-phenylethanol (2 in the presence of the immobilized enzyme, and could be used in 0.05 mol% with high efficiency. Commercially available isopropenyl acetate was employed as acylating agent in the lipase-catalyzed transesterifications, which makes the purification of the product very easy. In a successful large-scale DKR of 2, with 0.05 mol% of 1, (R-1-phenylethanol acetate (3 was obtained in 159 g (97% yield in excellent enantiomeric excess (99.8% ee.

Understanding LiOH chemistry in a ruthenium-catalyzed Li-O{sub 2} battery

Energy Technology Data Exchange (ETDEWEB)

Liu, Tao; Liu, Zigeng; Kim, Gunwoo; Grey, Clare P. [Department of Chemistry, University of Cambridge (United Kingdom); Frith, James T.; Garcia-Araez, Nuria [Department of Chemistry, University of Southampton (United Kingdom)

2017-12-11

Non-aqueous Li-O{sub 2} batteries are promising for next-generation energy storage. New battery chemistries based on LiOH, rather than Li{sub 2}O{sub 2}, have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru-catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4 e{sup -} oxygen reduction reaction, the H in LiOH coming solely from added H{sub 2}O and the O from both O{sub 2} and H{sub 2}O. On charging, quantitative LiOH oxidation occurs at 3.1 V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li{sub 2}O{sub 2}, LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long-lived battery. An optimized metal-catalyst-electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Isolation of a Bis-Iodurated Tetra-THF as a Trace Product from the Oxidation of Squalene with RuO4 and Its Double Ring Expansion to a Novel bis-THF-bis-THP Compound

Directory of Open Access Journals (Sweden)

Nicola Borbone

2011-06-01

Full Text Available A novel bis-iodurated polyether compound, based on an unprecedented tetra-THF backbone, has been isolated as a trace by-product of the oxidation of squalene with the catalytic system RuO2(cat./NaIO4. The double erythro configuration of the central portion of the molecule furnishes the first indirect support of the previously postulated pathway operating in the oxidative pentacyclization of the isoprenoid substrate. A bidirectional double oxidative bis-cyclization is invoked to explain the formation of this compound. The isolated substance was successfully subjected to a double rearrangement-ring expansion to give a novel bis-THF-bis-THP compound.

Preparation and characterization of Pt/C and Pt sbnd Ru/C electrocatalysts for direct ethanol fuel cells

Science.gov (United States)

Liu, Zhaolin; Ling, Xing Yi; Su, Xiaodi; Lee, Jim Yang; Gan, Leong Ming

Nano-sized Pt and Pt sbnd Ru colloids are prepared by a microwave-assisted polyol process, and transferred to a toluene solution of decanthiol. Vulcan XC-72 is then added to the toluene solution to adsorb the thiolated Pt and Pt sbnd Ru colloids. Transmission electron microscopy examinations show nearly spherical particles and narrow size distributions for both supported and unsupported metals. The carbon-supported Pt and Pt sbnd Ru nanoparticles are activated by thermal treatment to remove the thiol stabilizing shell. All Pt and Pt sbnd Ru catalysts (except Pt 23sbnd Ru 77) give the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure, whereas the Pt 23sbnd Ru 77 alloy is more typical of the hexagonal close packed (hcp) structure. The electro-oxidation of liquid ethanol on these catalysts is investigated at room temperature by cyclic voltammetry. The results demonstrate that the alloy catalyst is catalytically more active than pure platinum. Preliminary tests on a single cell of a direct ethanol fuel cell (DEFC) indicate that a Pt 52sbnd Ru 48/C anode catalyst gives the best electrocatalytic performance among all the carbon-supported Pt and Pt sbnd Ru catalysts.

Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

Science.gov (United States)

Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

2015-07-01

Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly

ROMP-Derived cyclooctene-based monolithic polymeric materials reinforced with inorganic nanoparticles for applications in tissue engineering

Directory of Open Access Journals (Sweden)

Franziska Weichelt

2010-12-01

Full Text Available Porous monolithic inorganic/polymeric hybrid materials have been prepared via ring-opening metathesis copolymerization starting from a highly polar monomer, i.e., cis-5-cyclooctene-trans-1,2-diol and a 7-oxanorborn-2-ene-derived cross-linker in the presence of porogenic solvents and two types of inorganic nanoparticles (i.e., CaCO3 and calcium hydroxyapatite, respectively using the third-generation Grubbs initiator RuCl2(Py2(IMesH2(CHPh. The physico-chemical properties of the monolithic materials, such as pore size distribution and microhardness were studied with regard to the nanoparticle type and content. Moreover, the reinforced monoliths were tested for the possible use as scaffold materials in tissue engineering, by carrying out cell cultivation experiments with human adipose tissue-derived stromal cells.

Triple Quenching of a Novel Self-Enhanced Ru(II) Complex by Hemin/G-Quadruplex DNAzymes and Its Potential Application to Quantitative Protein Detection.

Science.gov (United States)

Zhao, Min; Liao, Ni; Zhuo, Ying; Chai, Ya-Qin; Wang, Ji-Peng; Yuan, Ruo

2015-08-04

Herein, a novel "on-off" electrochemiluminescence (ECL) aptasensor for highly sensitive determination of thrombin has been constructed based on the triple quenching of the effect of hemin/G-quadruplex DNAzymes upon the Ru(II) complex-based ECL system. First, a strong initial ECL signal was achieved by the dual amplification strategies of (i) intramolecular coreaction of a self-enhanced Ru(II)-based molecule (PTCA-PEI-Ru(II)) and (ii) intermolecular coreaction between PTCA-PEI-Ru(II) and nicotinamide adenine dinucleotide (NADH), which was named the signal-on state. Then, a novel triple quenching of the effect of multifunctional hemin/G-quadruplex DNAzymes upon the Ru(II) complex-based ECL system was designed to realize the desirable signal-off state, which was outlined as follows: (i) the hemin/G-quadruplex DNAzymes mimicked NADH oxidase to oxidize NADH and in situ generate the H2O2, consuming the coreactant of NADH; (ii) its active center of hemin could oxidize the excited state PTCA-PEI-Ru(II)* to PTCA-PEI-Ru(III), making the energy and electron transfer quench; (iii) it also acted as horseradish peroxidase (HRP) to catalyze the H2O2 for in situ producing the quencher of O2. Based on triple quenching of the effect of hemin/G-quadruplex DNAzymes, the highly sensitive "on-off" thrombin aptasensor was developed with a wide linear detection range of 1.0 × 10(-14) M to 1.0 × 10(-10) M and a detection limit down to the femtomolar level.

Platinum Catalyzed Ring-Opening of 1,2-Cyclopropanated Sugars with O-Nucleophiles

DEFF Research Database (Denmark)

Beyer, Jürgen; Skaanderup, Philip Robert; Madsen, Robert

1999-01-01

In the presence of a catalytic amount of Zeise's dimer 1,2-cyclopropanated sugars undergo regioselective ring-opening at C-1 with O-nucleophiles including alcohols, phenols and water to produce 2-C-branched carbohydrates.......In the presence of a catalytic amount of Zeise's dimer 1,2-cyclopropanated sugars undergo regioselective ring-opening at C-1 with O-nucleophiles including alcohols, phenols and water to produce 2-C-branched carbohydrates....

Selectivity control in pd-catalyzed c-h functionalization reactions

OpenAIRE

Flores Gaspar, Areli

2013-01-01

Benzocyclobutenones are an intriguing four-membered ring ketone. In the present thesis, we have developed a new protocol for selectively preparing benzocyclobutenones through intramolecular acylation of aryl bromides via palladium catalyzed C-H bond functionalization reactions based on rac-BINAP ligand. We also found that a subtle modification on the ligand backbone lead to a new catalytic manifold for preparing configurationally-pure styrene derivatives, when using dcpp (bis-dicyclohexylphos...

Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

Science.gov (United States)

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

2018-05-21

The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

Electrodeposition of Pt-Ru nanoparticles on fibrous carbon substrates in the presence of nonionic surfactant: Application for methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W. [Department of Chemical and Biological Engineering, University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

2006-07-28

Liquid crystalline and micellar aqueous solutions of the nonionic surfactant Triton X-100 were used to direct the electrodeposition of Pt-Ru nanoparticles onto graphite felts, which were investigated as novel anodes for the direct methanol fuel cell. The effects of surfactant concentration, current density and deposition time in the preparation of these three-dimensional electrodes were studied in a factorial experiment and the electrodes were characterized by SEM and ICP-AES. Cyclic voltammetry, chronoamperometry and chronopotentiometry were carried out to assess the activity of the catalyzed felts for methanol oxidation. The presence of Triton X-100 (40-60wt.%) coupled with an acidic plating solution were essential for the efficient co-electrodeposition of Ru in the presence of Pt to yield approximately a 1:1 Pt:Ru atomic ratio in the deposit. The highest mass specific activity, 24Ag{sup -1} at 298K (determined by chronoamperometry after 180s at 0V versus Hg/Hg{sub 2}SO{sub 4}, K{sub 2}SO{sub 4std}), was obtained for the Pt-Ru electrodeposited in the presence of 40wt.% Triton X-100 at 60Am{sup -2}, 298K for 90min. Surfactant mediated electrodeposition is a promising method for meso-scale (ca. 10-60nm diameter) catalyst particle preparation on three-dimensional electrodes. (author)

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.

Quantum interference of ballistic carriers in one-dimensional semiconductor rings

International Nuclear Information System (INIS)

Bagraev, N.T.; Buravlev, A.D.; Klyachkin, L.E.; Malyarenko, A.M.; Ivanov, V.K.; Rykov, S.A.; Shelykh, I.A.

2000-01-01

Quantum interference of ballistic carriers has been studied for the first time, using one-dimensional rings formed by quantum wire pairs in self-assembled silicon quantum wells. Energy dependencies of the transmission coefficient is calculated as a function of the length and modulation of the quantum wire pairs separated by a unified drain-source system or the quantum point contacts. The quantum conductance is predicted to be increased by a factor of four using the unified drain-source system as a result of the quantum interference. Theoretical dependencies are revealed by the quantum conductance oscillations created by the deviations of both the drain-source voltage and external magnetic field inside the silicon one-dimensional rings. The results obtained put forward a basis to create the Aharonov-Bohm interferometer using the silicon one-dimensional ring [ru

Photoassisted Oxidation of Sulfides Catalyzed by Artificial Metalloenzymes Using Water as an Oxygen Source †

Directory of Open Access Journals (Sweden)

Christian Herrero

2016-12-01

Full Text Available The Mn(TpCPP-Xln10A artificial metalloenzyme, obtained by non-covalent insertion of Mn(III-meso-tetrakis(p-carboxyphenylporphyrin [Mn(TpCPP, 1-Mn] into xylanase 10A from Streptomyces lividans (Xln10A as a host protein, was found able to catalyze the selective photo-induced oxidation of organic substrates in the presence of [RuII(bpy3]2+ as a photosensitizer and [CoIII(NH35Cl]2+ as a sacrificial electron acceptor, using water as oxygen atom source.

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....

Atomistic growth phenomena of reactively sputtered RuO2 and MnO2 thin films

International Nuclear Information System (INIS)

Music, Denis; Bliem, Pascal; Geyer, Richard W.; Schneider, Jochen M.

2015-01-01

We have synthesized RuO 2 and MnO 2 thin films under identical growth conditions using reactive DC sputtering. Strikingly different morphologies, namely, the formation of RuO 2 nanorods and faceted, nanocrystalline MnO 2 , are observed. To identify the underlying mechanisms, we have carried out density functional theory based molecular dynamics simulations of the growth of one monolayer. Ru and O 2 molecules are preferentially adsorbed at their respective RuO 2 ideal surface sites. This is consistent with the close to defect free growth observed experimentally. In contrast, Mn penetrates the MnO 2 surface reaching the third subsurface layer and remains at this deep interstitial site 3.10 Å below the pristine surface, resulting in atomic scale decomposition of MnO 2 . Due to this atomic scale decomposition, MnO 2 may have to be renucleated during growth, which is consistent with experiments

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)

Metabolism and dosimetry of 106Ru inhaled as 106RuO4 by beagle dogs

International Nuclear Information System (INIS)

Snipes, M.B.

1981-01-01

This report provides metabolism and dosimetry data for inhaled ruthenium developed from studies in Beagle dogs that were exposed by inhalation to 106 RuO 4 . Twenty-six dogs were exposed nose-only to 106 RuO 4 and sacrificed at times from 2 hr to 512 days after inhalation exposure. Ninety-nine percent of the initial body burden was retained with an effective half-time of 1.2 days, 0.7% with a half-time of 14 days and 0.3% with a half-time of 170 days. Initial deposition was primarily in the nasopharyngeal and tracheobronchial regions. Results for deposition and retention of 106 Ru inhaled as 106 RuO 4 in dogs were similar to what has been observed for humans. The data for dogs were used to develop a model to predict potential radiation exposure patterns for humans after inhalation exposure to 106 RuO 4 . The model indicates that for humans the nasopharyngeal region, lower large intestine, and tracheobronchial epithelium would receive approx. 36, 13 and 10 times, respectively, the dose to 500 days after inhalation exposure to 106 RuO 4 that the lung would receive. The nasopharyngeal region should be considered the critical region for inhalation exposures to 106 RuO 4 . (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

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.

Inelastic scattering on 100Ru

International Nuclear Information System (INIS)

Sirota, S.

1987-01-01

Aspects of the nuclear structure of 100 Ru whe investigated by means of the scattering of 100 Ru (p,p') 100 Ru* with 16 MeV protons, where 21 states were investigated. The emergent protons were analysed by a magnetic spectrograph, of the enge type with a typical resolution of ≅ 9 KeV. (A.C.A.S.) [pt

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic bond tuning with heterocyclic carbenes

KAUST Repository

Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Jacobsen, Heiko

2013-01-01

have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions

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.

Development of closed cycle infrastructure at VNIPIET

International Nuclear Information System (INIS)

Onufrienko, S.V.; Kuzin, A.S.; Shafrova, N.P.; Zavadskij, M.I.

2012-01-01

Background to the creation of a closed nuclear fuel cycle is described. Achievements and future development projects of the Leading Institute VNIPIET are listed. The diagram of the closed nuclear fuel cycle in Russia with separate uranium and plutonium recycling is given. The major milestones of the VNIPIET history are reported [ru

New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

Energy Technology Data Exchange (ETDEWEB)

Huang, Qinhua [Iowa State Univ., Ames, IA (United States)

2004-12-19

The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I₂, ICl, PhSeCl, PhSCl and p-O₂NC₆H₄SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source.

Science.gov (United States)

Tong, Wenting; Cao, Pei; Liu, Yanhong; Chen, Jianxin

2017-11-03

Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.

Laser Spectroscopy of Ruthenium Containing Diatomic Molecules: RuH/D and RuP.

Science.gov (United States)

Adam, Allan G.; Konder, Ricarda M.; Nickerson, Nicole M.; Linton, Colan; Tokaryk, D. W.

2015-06-01

In the last few years, the Cheung group in Hong Kong and the Steimle group in Arizona have successfully studied several ruthenium containing diatomic molecules, RuX (X =C, O, N, B, using the laser-ablation molecular jet technique. Based on this success, the UNB spectroscopy group decided to try and find the optical signatures of other RuX molecules. Using CH_3OH and PH_3 as reactant gases, the RuH and RuP diatomic molecules have been detected in surveys of the 420 - 675 nm spectral region. RuD has also been made using fully deuterated methanol as a reactant. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra for these molecules have also been taken and the analysis is proceeding. The most recent results will be presented. F. Wang et al., Journal of Chemical Physics 139, 174318 (2013). N. Wang et al., Journal of Physical Chemistry A 117, 13279 (2013). T. Steimle et al., Journal of Chemical Physics 119, 12965 (2003). N. Wang et al., Chemical Physics Letters 547, 21 (2012).

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}.

Ring Expansion and Rearrangements of Rhodium(II) Azavinyl Carbenes

Science.gov (United States)

Selander, Nicklas; Worrell, Brady T.

2013-01-01

An efficient, regioselective and convergent method for the ring expansion and rearrangement of 1-sulfonyl-1,2,3-triazoles under rhodium(II)-catalyzed conditions is described. These denitrogenative reactions form substituted enaminone and olefin-based products, which in the former case can be further functionalized to unique products rendering the sulfonyl triazole traceless. PMID:23161725

Closed worlds and baryon asymmetry of the visible Universe

International Nuclear Information System (INIS)

Beletsky, Yu.A.

1980-01-01

In the early Universe the large scale perturbations of energy density can form closed worlds (topological decay of the initial Universe). Due to fluctuations of density of baryonic charge these closed worlds are charge asymmetrical even if the initial Universe was symmetric [ru

Thermodynamic assessment of the Al-Ru system

CSIR Research Space (South Africa)

Prins, SN

2003-03-01

Full Text Available describes the order disorder transformation with one Gibbs energy function. The RuAl6 phase was described as a stoichiometric phase and the remaining intermetallic phases (Ru4Al13, RuAl2 and Ru2Al3) were modelled with the sublattice model. The solubility...

Mechanism and the origins of stereospecificity in copper-catalyzed ring expansion of vinyl oxiranes: a traceless dual transition-metal-mediated process.

Science.gov (United States)

Mustard, Thomas J L; Mack, Daniel J; Njardarson, Jon T; Cheong, Paul Ha-Yeon

2013-01-30

Density functional theory computations of the Cu-catalyzed ring expansion of vinyloxiranes is mediated by a traceless dual Cu(I)-catalyst mechanism. Overall, the reaction involves a monomeric Cu(I)-catalyst, but a single key step, the Cu migration, requires two Cu(I)-catalysts for the transformation. This dual-Cu step is found to be a true double Cu(I) transition state rather than a single Cu(I) transition state in the presence of an adventitious, spectator Cu(I). Both Cu(I) catalysts are involved in the bond forming and breaking process. The single Cu(I) transition state is not a stationary point on the potential energy surface. Interestingly, the reductive elimination is rate-determining for the major diastereomeric product, while the Cu(I) migration step is rate-determining for the minor. Thus, while the reaction requires dual Cu(I) activation to proceed, kinetically, the presence of the dual-Cu(I) step is untraceable. The diastereospecificity of this reaction is controlled by the Cu migration step. Suprafacial migration is favored over antarafacial migration due to the distorted Cu π-allyl in the latter.

(15)N NMR spectroscopy unambiguously establishes the coordination mode of the diimine linker 2-(2'-pyridyl)pyrimidine-4-carboxylic acid (cppH) in Ru(ii) complexes.

Science.gov (United States)

Battistin, Federica; Balducci, Gabriele; Demitri, Nicola; Iengo, Elisabetta; Milani, Barbara; Alessio, Enzo

2015-09-21

We investigated the reactivity of three Ru(ii) precursors -trans,cis,cis-[RuCl2(CO)2(dmso-O)2], cis,fac-[RuCl2(dmso-O)(dmso-S)3], and trans-[RuCl2(dmso-S)4] - towards the diimine linker 2-(2'-pyridyl)pyrimidine-4-carboxylic acid (cppH) or its parent compound 4-methyl-2-(2'-pyridyl)pyrimidine ligand (mpp), in which a methyl group replaces the carboxylic group on the pyrimidine ring. In principle, both cppH and mpp can originate linkage isomers, depending on how the pyrimidine ring binds to ruthenium through the nitrogen atom ortho (N(o)) or para (N(p)) to the group in position 4. The principal aim of this work was to establish a spectroscopic fingerprint for distinguishing the coordination mode of cppH/mpp also in the absence of an X-ray structural characterization. By virtue of the new complexes described here, together with the others previously reported by us, we successfully recorded {(1)H,(15)N}-HMBC NMR spectra at natural abundance of the (15)N isotope on a consistent number of fully characterized Ru(ii)-cppH/mpp compounds, most of them being stereoisomers and/or linkage isomers. Thus, we found that (15)N NMR chemical shifts unambiguously establish the binding mode of cppH and mpp - either through N(o) or N(p)- and can be conveniently applied also in the absence of the X-ray structure. In fact, coordination of cppH to Ru(ii) induces a marked upfield shift for the resonance of the N atoms directly bound to the metal, with coordination induced shifts (CIS) ranging from ca.-45 to -75 ppm, depending on the complex, whereas the unbound N atom resonates at a frequency similar to that of the free ligand. Similar results were found for the complexes of mpp. This work confirmed our previous finding that cppH has no binding preference, whereas mpp binds exclusively through N(p). Interestingly, the two cppH linkage isomers trans,cis-[RuCl2(CO)2(cppH-κN(p))] (5) and trans,cis-[RuCl2(CO)2(cppH-κN(o))] (6) were easily obtained in pure form by exploiting their different

Rice cytochrome P450 MAX1 homologs catalyze distinct steps in strigolactone biosynthesis

KAUST Repository

Zhang, Yanxia; van Dijk, Aalt D J; Scaffidi, Adrian; Flematti, Gavin R.; Hofmann, Manuel; Charnikhova, Tatsiana; Verstappen, Francel; Hepworth, Jo; van der Krol, Sander; Leyser, Ottoline; Smith, Steven M.; Zwanenburg, Binne; Al-Babili, Salim; Ruyter-Spira, Carolien; Bouwmeester, Harro J.

2014-01-01

Strigolactones (SLs) are a class of phytohormones and rhizosphere signaling compounds with high structural diversity. Three enzymes, carotenoid isomerase DWARF27 and carotenoid cleavage dioxygenases CCD7 and CCD8, were previously shown to convert all-trans-β-carotene to carlactone (CL), the SL precursor. However, how CL is metabolized to SLs has remained elusive. Here, by reconstituting the SL biosynthetic pathway in Nicotiana benthamiana, we show that a rice homolog of Arabidopsis More Axillary Growth 1 (MAX1), encodes a cytochrome P450 CYP711 subfamily member that acts as a CL oxidase to stereoselectively convert CL into ent-2'-epi-5-deoxystrigol (B-C lactone ring formation), the presumed precursor of rice SLs. A protein encoded by a second rice MAX1 homolog then catalyzes the conversion of ent-2'-epi-5-deoxystrigol to orobanchol. We therefore report that two members of CYP711 enzymes can catalyze two distinct steps in SL biosynthesis, identifying the first enzymes involved in B-C ring closure and a subsequent structural diversification step of SLs.

Rice cytochrome P450 MAX1 homologs catalyze distinct steps in strigolactone biosynthesis

KAUST Repository

Zhang, Yanxia

2014-10-26

Strigolactones (SLs) are a class of phytohormones and rhizosphere signaling compounds with high structural diversity. Three enzymes, carotenoid isomerase DWARF27 and carotenoid cleavage dioxygenases CCD7 and CCD8, were previously shown to convert all-trans-β-carotene to carlactone (CL), the SL precursor. However, how CL is metabolized to SLs has remained elusive. Here, by reconstituting the SL biosynthetic pathway in Nicotiana benthamiana, we show that a rice homolog of Arabidopsis More Axillary Growth 1 (MAX1), encodes a cytochrome P450 CYP711 subfamily member that acts as a CL oxidase to stereoselectively convert CL into ent-2\\'-epi-5-deoxystrigol (B-C lactone ring formation), the presumed precursor of rice SLs. A protein encoded by a second rice MAX1 homolog then catalyzes the conversion of ent-2\\'-epi-5-deoxystrigol to orobanchol. We therefore report that two members of CYP711 enzymes can catalyze two distinct steps in SL biosynthesis, identifying the first enzymes involved in B-C ring closure and a subsequent structural diversification step of SLs.

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)

Modeling of lipase catalyzed ring-opening polymerization of epsilon-caprolactone.

Science.gov (United States)

Sivalingam, G; Madras, Giridhar

2004-01-01

Enzymatic ring-opening polymerization of epsilon-caprolactone by various lipases was investigated in toluene at various temperatures. The determination of molecular weight and structural identification was carried out with gel permeation chromatography and proton NMR, respectively. Among the various lipases employed, an immobilized lipase from Candida antartica B (Novozym 435) showed the highest catalytic activity. The polymerization of epsilon-caprolactone by Novozym 435 showed an optimal temperature of 65 degrees C and an optimum toluene content of 50/50 v/v of toluene and epsilon-caprolactone. As lipases can degrade polyesters, a maximum in the molecular weight with time was obtained due to the competition of ring opening polymerization and degradation by specific chain end scission. The optimum temperature, toluene content, and the variation of molecular weight with time are consistent with earlier observations. A comprehensive model based on continuous distribution kinetics was developed to model these phenomena. The model accounts for simultaneous polymerization, degradation and enzyme deactivation and provides a technique to determine the rate coefficients for these processes. The dependence of these rate coefficients with temperature and monomer concentration is also discussed.

Oxidation study of Cr-Ru hard coatings

Energy Technology Data Exchange (ETDEWEB)

Chen, Yung-I, E-mail: yichen@mail.ntou.edu.tw; Kuo, Yu-Chu; Chen, Sin-Min

2012-01-01

Cr-Ru alloy coatings with Cr content ranging from 47 to 83 at.% were deposited at 400 Degree-Sign C by direct current magnetron co-sputtering with a Ti interlayer on silicon substrates. With a total input power of 300 W, the Cr content in the Cr-Ru coatings increased linearly with the increasing input power of Cr. The intermetallic compound phase Cr{sub 2}Ru with columnar structure was identified for the as-deposited Cr{sub 56}Ru{sub 44} and Cr{sub 65}Ru{sub 35} coatings, resulting in an increase of hardness up to 15-16 GPa. To evaluate the performance of Cr-Ru coatings as a protective coating on glass molding dies, the annealing treatment was conducted at 600 Degree-Sign C in a 50 ppm O{sub 2}-N{sub 2} atmosphere. The outward diffusion and preferential oxidization of Cr in the Cr-Ru coatings resulted in the variations of the crystalline structure, chemical composition distribution, and surface hardness after annealing. X-ray diffraction and transmission electron microscopy (TEM) proved that an oxide scale consisting of Cr{sub 2}O{sub 3} formed on the free surface. Scanning electron microscopy and TEM observed the surface morphology and structural variation. The chemical composition depth profiles were analyzed by Auger electron microscopy, verifying the presence of a Cr-depleted zone beneath the oxide scale. The hardness of Cr{sub 56}Ru{sub 44} and Cr{sub 65}Ru{sub 35} coatings decreased to 11-12 GPa after annealing, accompanied by the replacement of the Cr{sub 2}Ru phase by the Ru phase. - Highlights: Black-Right-Pointing-Pointer We prepared crystalline Cr-Ru alloy coatings by direct current magnetron sputtering. Black-Right-Pointing-Pointer Cr-Ru coatings were annealed at 600 Degree-Sign C for 2 h in a 50 ppm O{sub 2}-N{sub 2} atmosphere. Black-Right-Pointing-Pointer Cr diffused outwardly and oxidized to form a stable and protective oxide scale. Black-Right-Pointing-Pointer The original columnar grains recrystallized to polycrystalline grains.

RuO4-mediated oxidation of secondary amines: Part 1. Are hydroxylamines main intermediates?

Directory of Open Access Journals (Sweden)

Florea Cristina A.

2016-01-01

Full Text Available The RuO4-catalyzed oxidation of secondary amines Bn-NH-CH2R (1a-b; R=H, Me gave mainly amides, but minute amounts of nitrones PhCH=N(O-CH2R (9a-b and traces of Bn-N(OH-CH2R (R=H, 4a were also detected. In the presence of cyanide, up to 22 reaction products were identified, but mainly α-aminonitriles. Comparison of the oxidation products of 1a-b with those of 4a-b, 9a-b, and Bn-N(O=CHR (10a-b showed that 4a-b cannot be main reaction intermediates formed from 1a-b.

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.

Concise copper-catalyzed synthesis of tricyclic biaryl ether-linked aza-heterocyclic ring systems.

Science.gov (United States)

Mestichelli, Paola; Scott, Matthew J; Galloway, Warren R J D; Selwyn, Jamie; Parker, Jeremy S; Spring, David R

2013-11-01

A new method for the synthesis of tricyclic biaryl ether-linked ring systems incorporating seven-, eight-, and nine-membered ring amines is presented. In the presence of catalytic quantities of copper(I), readily accessible acyclic precursors undergo an intramolecular carbon-oxygen bond-forming reaction facilitated by a "templating" chelating nitrogen atom. The methodology displays a broad substrate scope, is practical, and generates rare and biologically interesting tricyclic heteroaromatic products that are difficult to access by other means.

Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

Energy Technology Data Exchange (ETDEWEB)

Bauer, Alex; Gyenge, Elod L.; Oloman, Colin W. [Department of Chemical and Biological Engineering, The University of British Columbia, 2360 East Mall, Vancouver, BC (Canada)

2007-05-15

Pressed graphite felt (thickness {proportional_to}350 {mu}m) with electrodeposited PtRu (43 g m{sup -2}, 1.4:1 atomic ratio) or PtRuMo (52 g m{sup -2}, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m{sup -2} with PtRuMo at 5500 A m{sup -2} and 353 K while under the same conditions PtRu yielded 1925 W m{sup -2}. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation. (author)

Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

Science.gov (United States)

Bauer, Alex; Gyenge, Előd L.; Oloman, Colin W.

Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

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.

Water oxidation catalyzed by mononuclear ruthenium complexes with a 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand: how ligand environment influences the catalytic behavior.

Science.gov (United States)

Staehle, Robert; Tong, Lianpeng; Wang, Lei; Duan, Lele; Fischer, Andreas; Ahlquist, Mårten S G; Sun, Licheng; Rau, Sven

2014-02-03

A new water oxidation catalyst [Ru(III)(bda)(mmi)(OH2)](CF3SO3) (2, H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; mmi = 1,3-dimethylimidazolium-2-ylidene) containing an axial N-heterocyclic carbene ligand and one aqua ligand was synthesized and fully characterized. The kinetics of catalytic water oxidation by 2 were measured using stopped-flow technique, and key intermediates in the catalytic cycle were probed by density functional theory calculations. While analogous Ru-bda water oxidation catalysts [Ru(bda)L2] (L = pyridyl ligands) are supposed to catalyze water oxidation through a bimolecular coupling pathway, our study points out that 2, surprisingly, undergoes a single-site water nucleophilic attack (acid-base) pathway. The diversion of catalytic mechanisms is mainly ascribed to the different ligand environments, from nonaqua ligands to an aqua ligand. Findings in this work provide some critical proof for our previous hypothesis about how alternation of ancillary ligands of water oxidation catalysts influences their catalytic efficiency.

Optimum Pt and Ru atomic composition of carbon-supported Pt-Ru alloy electrocatalyst for methanol oxidation studied by the polygonal barrel-sputtering method

International Nuclear Information System (INIS)

Hiromi, Chikako; Inoue, Mitsuhiro; Taguchi, Akira; Abe, Takayuki

2011-01-01

Highlights: → The sputtered Pt and Ru form the Pt-Ru alloy nanoparticles on the carbon support. → The deposited Pt-Ru alloy particles have uniform Pt:Ru atomic ratios. → The optimum Pt:Ru ratio of the Pt-Ru/C for methanol oxidation is 58:42 at.% at 25 deg. C. → The optimum Pt:Ru ratio of 58:42 shifts to 50:50 at.% at 40 and 60 deg. C. → The polygonal barrel-sputtering method is useful to prepare the DMFC anode catalyst. - Abstract: The optimum Pt and Ru atomic composition of a carbon-supported Pt-Ru alloy (Pt-Ru/C) used in a practical direct methanol fuel cell (DMFC) anode was investigated. The samples were prepared by the polygonal barrel-sputtering method. Based on the physical properties of the prepared Pt-Ru/C samples, the Pt-Ru alloy was found to be deposited on a carbon support. The microscopic characterization showed that the deposited alloy forms nanoparticles, of which the atomic ratios of Pt and Ru (Pt:Ru ratios) are uniform and are in accordance with the overall Pt:Ru ratios of the samples. The formation of the Pt-Ru alloy is also supported by the electrochemical characterization. Based on these results, methanol oxidation on the Pt-Ru/C samples was measured by cyclic voltammetry and chronoamperometry. The results indicated that the methanol oxidation activities of the prepared samples depended on the Pt:Ru ratios, of which the optimum Pt:Ru ratio is 58:42 at.% at 25 deg. C and 50:50 at.% at 40 and 60 deg. C. This temperature dependence of the optimum Pt:Ru ratio is well explained by the relationship between the methanol oxidation reaction process and the temperature, which is reflected in the rate-determining steps considered from the activation energies. It should be noted that at 25-60 deg. C, the Pt-Ru/C with Pt:Ru = 50:50 at.% prepared by our sputtering method has the higher methanol oxidation activity than that of a commercially available sample with the identical overall Pt:Ru ratio. Consequently, the polygonal barrel-sputtering method

Copper-catalyzed asymmetric ring opening of oxabicyclic alkenes with organolithium reagents

NARCIS (Netherlands)

Bos, Pieter H.; Rudolph, Alena; Pérez, Manuel; Fañanás-Mastral, Martín; Harutyunyan, Syuzanna R.; Feringa, Bernard

2012-01-01

A highly efficient method is reported for the asymmetric ring opening of oxabicyclic alkenes with organolithium reagents. Using a copper/chiral phosphoramidite complex together with a Lewis acid (BF3·OEt2), full selectivity for the anti isomer and excellent enantioselectivities were obtained for the

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

Sulfuric acid as a catalyst for ring-opening of biobased bis-epoxides

Science.gov (United States)

Vegetable oils can be relatively and easily transformed into bio-based epoxides. Because of this, the acid-catalyzed epoxide ring-opening has been explored for the preparation of bio-based lubricants and polymers. Detailed model studies are carried out only with mono-epoxide made from methyl oleate,...

In situ Ru K-edge EXAFS of CO adsorption on a Ru modified Pt/C fuel cell catalyst

International Nuclear Information System (INIS)

Rose, Abigail; Bilsborrow, Robert; King, Colin R.; Ravikumar, M.K.; Qian Yangdong; Wiltshire, Richard J.K.; Crabb, Eleanor M.; Russell, Andrea E.

2009-01-01

The Ru-CO bond of CO adsorbed on a Ru modified Pt/C fuel cell catalyst has been directly probed by in situ EXAFS at the Ru K-edge, providing evidence of a CO:metal surface atom ratio greater than 1:1 and that CO is adsorbed at bridging sites associated with Ru atoms at the surface of the catalyst nanoparticles. This result illustrates the limitations of single crystal models as representations of the bonding of adsorbed species at nanoparticle surfaces.

DNA gyrase with a single catalytic tyrosine can catalyze DNA supercoiling by a nicking-closing mechanism

Science.gov (United States)

Gubaev, Airat; Weidlich, Daniela; Klostermeier, Dagmar

2016-01-01

The topological state of DNA is important for replication, recombination and transcription, and is regulated in vivo by DNA topoisomerases. Gyrase introduces negative supercoils into DNA at the expense of ATP hydrolysis. It is the accepted view that gyrase achieves supercoiling by a strand passage mechanism, in which double-stranded DNA is cleaved, and a second double-stranded segment is passed through the gap, converting a positive DNA node into a negative node. We show here that gyrase with only one catalytic tyrosine that cleaves a single strand of its DNA substrate can catalyze DNA supercoiling without strand passage. We propose an alternative mechanism for DNA supercoiling via nicking and closing of DNA that involves trapping, segregation and relaxation of two positive supercoils. In contrast to DNA supercoiling, ATP-dependent relaxation and decatenation of DNA by gyrase lacking the C-terminal domains require both tyrosines and strand passage. Our results point towards mechanistic plasticity of gyrase and might pave the way for finding novel and specific mechanism-based gyrase inhibitors. PMID:27557712

Ni@Ru and NiCo@Ru Core-Shell Hexagonal Nanosandwiches with a Compositionally Tunable Core and a Regioselectively Grown Shell.

Science.gov (United States)

Hwang, Hyeyoun; Kwon, Taehyun; Kim, Ho Young; Park, Jongsik; Oh, Aram; Kim, Byeongyoon; Baik, Hionsuck; Joo, Sang Hoon; Lee, Kwangyeol

2018-01-01

The development of highly active electrocatalysts is crucial for the advancement of renewable energy conversion devices. The design of core-shell nanoparticle catalysts represents a promising approach to boost catalytic activity as well as save the use of expensive precious metals. Here, a simple, one-step synthetic route is reported to prepare hexagonal nanosandwich-shaped Ni@Ru core-shell nanoparticles (Ni@Ru HNS), in which Ru shell layers are overgrown in a regioselective manner on the top and bottom, and around the center section of a hexagonal Ni nanoplate core. Notably, the synthesis can be extended to NiCo@Ru core-shell nanoparticles with tunable core compositions (Ni 3 Co x @Ru HNS). Core-shell HNS structures show superior electrocatalytic activity for the oxygen evolution reaction (OER) to a commercial RuO 2 black catalyst, with their OER activity being dependent on their core compositions. The observed trend in OER activity is correlated to the population of Ru oxide (Ru 4+ ) species, which can be modulated by the core compositions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

Science.gov (United States)

Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

2010-05-17

Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

Pseudogap behavior of RuP probed by photoemission spectroscopy

OpenAIRE

Sato, K.; Ootsuki, D.; Wakisaka, Y.; Saini, N. L.; Mizokawa, T.; Arita, M.; Anzai, H.; Namatame, H.; Taniguchi, M.; Hirai, D.; Takagi, H.

2012-01-01

We have studied the electronic structure of RuP and related Ru pnictides using photoemission spectroscopy. Ru 3d core-level and valence-band spectra of RuP show that the Ru valence is +3 with t_{2g}^5 configuration. The photoemisson spectral weight near the Fermi level is moderately suppressed in the pseudogap phase of RuP, consistent with the pseudogap opening of 2\\Delta/k_BT_c ~ 3 (gap size \\Delta ~ 50 meV and transition temperature T_c ~ 330 K). The Ru 3d peak remains sharp in the pseudoga...

Total Synthesis of (R, R, R)-gamma-Tocopherol through Cu-Catalyzed Asymmetric 1,2-Addition

NARCIS (Netherlands)

Wu, Zhongtao; Harutyunyan, Syuzanna R.; Minnaard, Adriaan J.

2014-01-01

Based on the asymmetric copper-catalyzed 1,2-addition of Grignard reagents to ketones, (R,R,R)--tocopherol has been synthesized in 36% yield over 12 steps (longest linear sequence). The chiral center in the chroman ring was constructed with 73% ee by the 1,2-addition of a phytol-derived Grignard

Dienone-phenol Rearrangement of C-9 Oxygenated Decalinic Dienone and Analogs through B-Ring Cleavage

Institute of Scientific and Technical Information of China (English)

无

2003-01-01

Dehydrogenation of 9-hydroxy decalinic enones and analogs with DDQ resulted in a formal dienone-phenol type rearrangement via B-ring cleavage, while the corresponding dienone acetates underwent base-catalyzed formal dienone-phenol type rearrangement analogously.

Atomistic growth phenomena of reactively sputtered RuO{sub 2} and MnO{sub 2} thin films

Energy Technology Data Exchange (ETDEWEB)

Music, Denis, E-mail: music@mch.rwth-aachen.de; Bliem, Pascal; Geyer, Richard W.; Schneider, Jochen M. [Materials Chemistry, RWTH Aachen University, Kopernikusstr. 10, 52074 Aachen (Germany)

2015-07-07

We have synthesized RuO{sub 2} and MnO{sub 2} thin films under identical growth conditions using reactive DC sputtering. Strikingly different morphologies, namely, the formation of RuO{sub 2} nanorods and faceted, nanocrystalline MnO{sub 2}, are observed. To identify the underlying mechanisms, we have carried out density functional theory based molecular dynamics simulations of the growth of one monolayer. Ru and O{sub 2} molecules are preferentially adsorbed at their respective RuO{sub 2} ideal surface sites. This is consistent with the close to defect free growth observed experimentally. In contrast, Mn penetrates the MnO{sub 2} surface reaching the third subsurface layer and remains at this deep interstitial site 3.10 Å below the pristine surface, resulting in atomic scale decomposition of MnO{sub 2}. Due to this atomic scale decomposition, MnO{sub 2} may have to be renucleated during growth, which is consistent with experiments.

Peierls-distorted Ru-chains and boron dumbbells in Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} from first-principles calculations and experiments

Energy Technology Data Exchange (ETDEWEB)

Touzani, Rachid S.; Mbarki, Mohammed; Chen, Ximeng [Institute of Inorganic Chemistry, RWTH Aachen University (Germany); Fokwa, Boniface P.T. [Institute of Inorganic Chemistry, RWTH Aachen University (Germany); Department of Chemistry, University of California Riverside (UCR), Riverside, CA (United States)

2016-09-15

Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} phases were recently predicted by GGA-VASP structure optimization to crystallize in the Nb{sub 2}OsB{sub 2}-type structure. Although the Fe-based (Mo{sub 2}FeB{sub 2} type) and Os-based (Nb{sub 2}OsB{sub 2} type, superstructure variant of Mo{sub 2}FeB{sub 2} type) analogues have been synthesized and characterized successfully, the Ru-based phases remained unknown. Crystal structure prediction of Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} phases, using an evolutionary algorithm, led to the AlMn{sub 2}B{sub 2}-type structure in contrast to the aforementioned optimization; however, phonon calculations showed that the Nb{sub 2}OsB{sub 2}-type phases are dynamically more stable than the AlMn{sub 2}B{sub 2}-type phases. A slightly modified synthetic strategy finally led to the successful preparation of the predicted phases. The extremely quick arc-melting procedure, under argon atmosphere, not only led to a quantitative amount of the phases but also to single crystals suitable for structure determination. Powder and single-crystal X-ray diffraction as well as EDX analysis of the metal ratio have confirmed the GGA-VASP structure optimization: Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} compounds indeed crystallize isotypically with Nb{sub 2}OsB{sub 2} structure, a superstructure variant of Mo{sub 2}FeB{sub 2} type, in which B-dumbbells and Peierls-distorted Ru-chains are found. Susceptibility measurements on a Ta{sub 2}RuB{sub 2} single crystal reveal no superconducting transition down to 2 K, even though some features in the band structures of both phases, similar to those reported in superconducting NbRuB, hinted at possible superconductivity. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Nonalloyed carbon-supported PtRu catalysts for PEMFC applications

NARCIS (Netherlands)

Papageorgopoulos, D.C.; Heer, de M.P.; Keijzer, M.; Pieterse, J.A.Z.; Bruijn, de F.A.

2004-01-01

PtRu(1:1)/C catalysts were prepared by a process that was claimed previously to lead to nonalloyed Pt and Ru particles, using twodifferent precursors, Ru nitrosyl nitrate and Ru chloride hydrate. Both X-ray diffraction and characterization by cyclic voltammetrypoint toward Pt and Ru being present as

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.

Surface studies by low energy ion beams: Cu/Ru(0001) and Cu/O/Ru(0001)

Energy Technology Data Exchange (ETDEWEB)

Shen, Y.G.; O`Connor, D.J.; MacDonald, R.J. [Newcastle Univ., NSW (Australia). Dept. of Physics; Wandelt, H. [Institut fur Physikalische und Theoretische Chemie der Universitat Bonn, Bonn (Germany).; Zee, H. van [Eindhoven University of Technology, Eindhoven (Netherlands) Dept. of Physics

1993-12-31

The surface structure of Cu on Ru(OOO1) has been studied by low energy Li{sup +} ion scattering. It was found that Cu forms pseudomorphic islands for two layers. The effects of Cu on an O-precovered RU(OOO1) surface has also been investigated using keV He{sup +} ions. The results show that during the deposition of Cu, O is displaced from the Ru surface and migrated onto the top of the surface of the growing overlayer. The floated out O has been tested, showing a disordered overlayer. 5 refs., 3 figs.

Surface studies by low energy ion beams: Cu/Ru(0001) and Cu/O/Ru(0001)

Energy Technology Data Exchange (ETDEWEB)

Shen, Y G; O` Connor, D J; MacDonald, R J [Newcastle Univ., NSW (Australia). Dept. of Physics; Wandelt, H [Institut fur Physikalische und Theoretische Chemie der Universitat Bonn, Bonn (Germany).; Zee, H van [Eindhoven University of Technology, Eindhoven (Netherlands) Dept. of Physics

1994-12-31

The surface structure of Cu on Ru(OOO1) has been studied by low energy Li{sup +} ion scattering. It was found that Cu forms pseudomorphic islands for two layers. The effects of Cu on an O-precovered RU(OOO1) surface has also been investigated using keV He{sup +} ions. The results show that during the deposition of Cu, O is displaced from the Ru surface and migrated onto the top of the surface of the growing overlayer. The floated out O has been tested, showing a disordered overlayer. 5 refs., 3 figs.

Nonalloyed carbon-supported PtRu catalysts for PEMFC applications

NARCIS (Netherlands)

Papageorgopoulos, D.C.; De Heer, M.P.; Keijzer, M.; Pieterse, J.A.Z.; de Bruijn, F. A.

2004-01-01

PtRu(1:1)/C catalysts were prepared by a process that was claimed previously to lead to non-alloyed Pt and Ru particles, using two different precursors, Ru nitrosyl nitrate and Ru chloride hydrate. Both X-ray diffraction and characterization by cyclic voltammetry point toward Pt and Ru being present

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.

Formation of graphene on Ru(0001) surface

Institute of Scientific and Technical Information of China (English)

Pan Yi; Shi Dong-Xia; Gao Hong-Jun

2007-01-01

We report on the formation of a graphene monolayer on a Ru(0001) surface by annealing the Ru(0001) crystal.The samples are characterized by scanning tunnelling microscopy (STM) and Auger electron spectroscopy (AES). STM images show that the Moiré pattern is caused by the graphene layer mismatched with the underlying Ru(0001) surface and has an N × N superlattice. It is further found that the graphene monolayer on a Ru(0001) surface is very stable at high temperatures. Our results provide a simple and convenient method to produce a graphene monolayer on the Ru(0001) surface, which is used as a template for fabricating functional nanostructures needed in future nano devices and catalysis.

Mechanistic evidence for a ring-opening pathway in the Pd-catalyzed direct arylation of benzoxazoles

DEFF Research Database (Denmark)

Sanchez, R.S.; Zhuravlev, Fedor

2007-01-01

The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent with the r......The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent...... with the rate-limiting electrophilic or concerted palladation. A mechanism, proposed on the basis of kinetic and computational studies, includes generation of isocyanophenolate as the key step. The DFT calculations suggest that the overall catalytic cycle is facile and is largely controlled by the C-H acidity...

Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

Science.gov (United States)

Ju, Minsoo; Weatherly, Cale D; Guzei, Ilia A; Schomaker, Jennifer M

2017-08-07

Asymmetric nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ru nanostructure fabrication using an anodic aluminum oxide nanotemplate and highly conformal Ru atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Kim, Woo-Hee; Park, Sang-Joon; Son, Jong-Yeog; Kim, Hyungjun [Department of Material Science and Engineering, POSTECH Pohang University of Science and Technology, San 31, Hyoja-Dong, Nam-Gu, Pohang 790-784 (Korea, Republic of)

2008-01-30

We fabricated metallic nanostructures directly on Si substrates through a hybrid nanoprocess combining atomic layer deposition (ALD) and a self-assembled anodic aluminum oxide (AAO) nanotemplate. ALD Ru films with Ru(DMPD)(EtCp) as a precursor and O{sub 2} as a reactant exhibited high purity and low resistivity with negligible nucleation delay and low roughness. These good growth characteristics resulted in the excellent conformality for nanometer-scale vias and trenches. Additionally, AAO nanotemplates were fabricated directly on Si and Ti/Si substrates through a multiple anodization process. AAO nanotemplates with various hole sizes (30-100 nm) and aspect ratios (2:1-20:1) were fabricated by controlling the anodizing process parameters. The barrier layers between AAO nanotemplates and Si substrates were completely removed by reactive ion etching (RIE) using BCl{sub 3} plasma. By combining the ALD Ru and the AAO nanotemplate, Ru nanostructures with controllable sizes and shapes were prepared on Si and Ti/Si substrates. The Ru nanowire array devices as a platform for sensor devices exhibited befitting properties of good ohmic contact and high surface/volume ratio.

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 ...

Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

DEFF Research Database (Denmark)

Maggi, Agnese; Madsen, Robert

2012-01-01

A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

Science.gov (United States)

Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

2006-05-25

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

Reactions of ethanol on Ru

NARCIS (Netherlands)

Sturm, Jacobus Marinus; Liu, Feng; Lee, Christopher James; Bijkerk, Frederik

2012-01-01

The adsorption and reactions of ethanol on Ru(0001) were studied with temperatureprogrammed desorption (TPD) and reflection-absorption infrared spectroscopy (RAIRS). Ethanol was found to adsorb intact onto Ru(0001) below 100 K. Heating to 250 K resulted in formation of ethoxy groups, which undergo

Ligand design for site-selective metal coordination: synthesis of transition-metal complexes with η{sup 6}-coordination of the central ring of anthracene

Energy Technology Data Exchange (ETDEWEB)

Karslyan, Eduard E.; Borissova, Alexandra O.; Perekalin, Dmitry S. [Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow (Russian Federation)

2017-05-08

A polycyclic aromatic ligand for site-selective metal coordination was designed by using DFT calculations. The computational prediction was confirmed by experiments: 2,3,6,7-tetramethoxy-9,10-dimethylanthracene initially reacts with [(C{sub 5}H{sub 5})Ru(MeCN){sub 3}]BF{sub 4} to give the kinetic product with a [(C{sub 5}H{sub 5})Ru]{sup +} fragment coordinated at the terminal ring, which is then transformed into the thermodynamic product with coordination through the central ring. These isomeric complexes have markedly different UV/Vis spectra, which was explained by analysis of the frontier orbitals. At the same time, the calculations suggest that electrostatic interactions are mainly responsible for the site selectivity of the coordination. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

International Nuclear Information System (INIS)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

2017-01-01

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

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.

Design, Synthesis and Biological Activity of Novel Reversible Peptidyl FVIIa Inhibitors Rh-Catalyzed Enantioselective Synthesis of Diaryl Amines

DEFF Research Database (Denmark)

Storgaard, Morten

functional group tolerance. Unfortunately, these -aryl tetramic acids were too unreactive and ring opening toward the synthesis of the building block did not succeed. However, -aryl tetramic acids are still interesting compounds due to their potential biological activity. The building block 3.15 (P1......-catalyzed enantioselective synthesis of diaryl amines, which is an important class of compounds (Chapter 4). For example it is found in the third generation anti-histaminic agent levocetirizine. Development of efficient synthetic routes is therefore of considerably interest. The rhodium-catalyzed enantioselective synthesis...

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

The annealing effects on the micro-structure and properties of RuMoC films as seedless barrier for advanced Cu metallization

Energy Technology Data Exchange (ETDEWEB)

Zou, Jianxiong; Liu, Bo, E-mail: liubo2009@scu.edu.cn, E-mail: gh.jiao@siat.ac.cn [Key Laboratory of Radiation Physics and Technology of Ministry of Education, Institute of Nuclear Science and Technology, Sichuan University, Chengdu 610064 (China); Jiao, Guohua, E-mail: liubo2009@scu.edu.cn, E-mail: gh.jiao@siat.ac.cn; Lu, Yuanfu; Dong, Yuming [Shenzhen Institutes of Advanced Technology Chinese Academy of Sciences, Shenzhen 518055 (China); The Chinese University of Hong Kong, Hong Kong (China); Li, Qiran [Institut d' Electronique Fondamentale, CNRS-Université Paris Sud UMR 8622, 91405 Orsay (France)

2016-09-07

100 nm thick RuMoC films and 5 nm thick RuMoC films with Cu capping have been deposited on Si(111) by magnetron co-sputtering with Ru and MoC confocal targets. The samples were subsequently annealed at temperatures ranging from 450 to 650 °C in vacuum at a pressure of 3 × 10{sup −4} Pa to study the annealing effects on the microstructures and properties of RuMoC films for advanced seedless Cu metallization applications. The sheet resistances, residual oxygen contents, and microstructures of the RuMoC films have close correlation with the doping contents of Mo and C, which can be easily controlled by the deposition power ratio of MoC versus Ru targets (DPR). When DPR was 0.5, amorphous RuMoC film (marked as RuMoC II) with low sheet resistances and residual oxygen contents was obtained. The fundamental relationship between the annealing temperatures with the microstructures and properties of the RuMoC films was investigated, and a critical temperature point was revealed at about 550 °C where the components and microstructures of the RuMoC II films changed obviously. Results indicated that below 550 °C, the RuMoC II films remained amorphous due to the well-preserved C-Ru and C-Mo bonds. However, above 550 °C, the microstructures of RuMoC II films transformed from amorphous to nano-composite structure due to the breakage of Ru-C bonds, while the supersaturated solid solution MoC segregated out along the grain boundaries of Ru, thus hindering the diffusion of Cu and O atoms. This is the main mechanism of the excellent thermal stability of the RuMoC films after annealing at high temperatures. The results indicated great prospects of amorphous RuMoC films in advanced seedless Cu metallization applications.

Oxidation of lignin-carbohydrate complex from bamboo with hydrogen peroxide catalyzed by Co(salen

Directory of Open Access Journals (Sweden)

Zhou Xue-Fei

2014-01-01

Full Text Available The reactivity of salen complexes toward hydrogen peroxide has been long recognized. Co(salen was tested as catalyst for the aqueous oxidation of a refractory lignin-carbohydrate complex (LCC isolated from sweet bamboo (Dendrocalamushamiltonii in the presence of hydrogen peroxide as oxidant. Co(salen catalyzed the reaction of hydrogen peroxide with LCC. From the spectra analyses, lignin units in LCC were undergoing ring-opening, side chain oxidation, demethoxylation, β-O-4 cleavage with Co(salen catalytic oxidation. The degradation was also observed in the carbohydrate of LCC. The investigation on the refractory LCC degradation catalyzed by Co(salen may be an important aspect for environmentally-oriented biomimetic bleaching in pulp and paper industry.

Synthesis process and structural characterization of the Sr{sub 2}EuRuO{sub 6} complex perovskite

Energy Technology Data Exchange (ETDEWEB)

Triana, C.A.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales (GFNM), Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 5997 (Colombia); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Fisica de Nuevos Materiales (GFNM), Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 5997 (Colombia)

2012-03-05

Highlights: Black-Right-Pointing-Pointer Crystal structure, surface morphology and composition of Sr{sub 2}EuRuO{sub 6} have been studied. Black-Right-Pointing-Pointer Sr{sub 2}EuRuO{sub 6} crystallize in a monoclinic perovskite-type structure in P2{sub 1}/n space group. Black-Right-Pointing-Pointer Ru{sup 5+} and Eu{sup 3+} ions are on the six coordinate M sites, Sr{sup 2+} is located in the A-site. Black-Right-Pointing-Pointer Scanning electron microscopy and Scherrer formula shows a particle size of D = 34.2 nm. Black-Right-Pointing-Pointer Activation energy Q through the Arrhenius plot for Sr{sub 2}EuRuO{sub 6} is close to 39.6 kJ/mol. - Abstract: The Sr{sub 2}EuRuO{sub 6} complex perovskite has been synthesized by the solid-state reaction method and the crystal structure, surface morphology and composition have been investigated. Results of powder X-ray diffraction measurements and Rietveld analysis show that this compound crystallizes in a monoclinic distorted perovskite-type structure, which belongs to the monoclinic P2{sub 1}/n (no. 14) space group, that corresponds to the (a{sup +}b{sup -}b{sup -}) tilt system on the Glazer notation. The structure presents an alternating distribution of the Ru{sup 5+} and Eu{sup 3+} ions on the six coordinate M sites, while the Sr{sup 2+} is located in the A-site of the Sr{sub 2}EuRuO{sub 6} complex perovskite, with lattice parameters a = 5.7996(5) Angstrom-Sign , b = 5.8960(7) Angstrom-Sign , c = 8.3234(6) Angstrom-Sign , angle {beta} = 90.234(7) Degree-Sign and V = 284.61(4) Angstrom-Sign {sup 3}. Morphological analysis of this material, performed by scanning electron microscopy (SEM), allows to establish the granular feature of compound with agglomerates from amongst Almost-Equal-To 1 to 3 {mu}m size, and by means of the Scherrer formula was calculated a particle size of D = 34.2 nm. Result suggests that crystal structure of the Sr{sub 2}EuRuO{sub 6} suffers grain size-induced polarization rotation, which produces a

A Renewable and Ultrasensitive Electrochemiluminescence Immunosenor Based on Magnetic RuL@SiO2-Au~RuL-Ab2 Sandwich-Type Nano-Immunocomplexes

Directory of Open Access Journals (Sweden)

Ning Gan

2011-08-01

Full Text Available An ultrasensitive and renewable electrochemiluminescence (ECL immunosensor was developed for the detection of tumor markers by combining a newly designed trace tag and streptavidin-coated magnetic particles (SCMPs. The trace tag (RuL@SiO2-Au~RuL-Ab2 was prepared by loading Ru(bpy32+(RuL-conjuged secondary antibodies (RuL-Ab2 on RuL@SiO2 (RuL-doped SiO2 doped Au (RuL@SiO2-Au. To fabricate the immunosensor, SCMPs were mixed with biotinylated AFP primary antibody (Biotin-Ab1, AFP, and RuL@SiO2-Au~RuL-Ab2 complexes, then the resulting SCMP/Biotin-Ab1/AFP/RuL@SiO2-Au~RuL-Ab2 (SBAR sandwich-type immunocomplexes were absorbed on screen printed carbon electrode (SPCE for detection. The immunocomplexes can be easily washed away from the surface of the SPCE when the magnetic field was removed, which made the immunosensor reusable. The present immunosensor showed a wide linear range of 0.05–100 ng mL–1 for detecting AFP, with a low detection limit of 0.02 ng mL–1 (defined as S/N = 3. The method takes advantage of three properties of the immunosensor: firstly, the RuL@SiO2-Au~RuL-Ab2 composite exhibited dual amplification since SiO2 could load large amount of reporter molecules (RuL for signal amplification. Gold particles could provide a large active surface to load more reporter molecules (RuL-Ab2. Accordingly, through the ECL response of RuL and tripropylamine (TPA, a strong ECL signal was obtained and an amplification analysis of protein interaction was achieved. Secondly, the sensor is renewable because the sandwich-type immunocomplexes can be readily absorbed or removed on the SPCE’s surface in a magnetic field. Thirdly, the SCMP modified probes can perform the rapid separation and purification of signal antibodies in a magnetic field. Thus, the present immunosensor can simultaneously realize separation, enrichment and determination. It showed potential application for the detection of AFP in human sera.

[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.

Round table on RU486.

Science.gov (United States)

Shallat, L

1993-01-01

As a non-invasive means of early abortion, RU-486 has the potential to increase women's reproductive options; at the same time, the "abortion pill" has stimulated debate about the ethics and safety of new medical technologies. When combined with a prostaglandin (PG), the success rate for RU-486 is 96% for pregnancies of up to 9 weeks' gestation. In France, over 120,000 women have used RU-486/PG to terminate pregnancy, and this regimen is now used in about 25% of abortions. Clinical trials of RU-486 are underway in Cuba, China, India, Singapore, and Zambia. The Program for Appropriate Technology has identified four considerations for introducing RU-486 to developing countries: whether abortion or menstrual regulation is legal; whether women find the method acceptable and can comply with the multiple visit treatment regimen; whether the health infrastructure can support safe method use, including prevention of misuse and provision of appropriate medical backup personnel and facilities; and whether the cost of the regimen is affordable to individuals and/or programs --conditions unlikely to be met in most such countries. Ideal would be development of a medical abortifacient that is single dose and the lowest possible dose of each drug, provokes miscarriage within a more predictable time frame with less acute and prolonged bleeding, is safe and effective beyond two months, has minimal side effects, and maximizes short-term safety and minimizes long-term effects. Technological advances are being undermined, however, by political and religious attacks on the method. Even some feminists have expressed concerns about potential long-term effects of RU-486 use.

Electrical Transport Signature of the Magnetic Fluctuation-Structure Relation in α-RuCl3 Nanoflakes.

Science.gov (United States)

Mashhadi, Soudabeh; Weber, Daniel; Schoop, Leslie M; Schulz, Armin; Lotsch, Bettina V; Burghard, Marko; Kern, Klaus

2018-05-09

The small gap semiconductor α-RuCl 3 has emerged as a promising candidate for quantum spin liquid materials. Thus far, Raman spectroscopy, neutron scattering, and magnetization measurements have provided valuable hints for collective spin behavior in α-RuCl 3 bulk crystals. However, the goal of implementing α-RuCl 3 into spintronic devices would strongly benefit from the possibility of electrically probing these phenomena. To address this, we first investigated nanoflakes of α-RuCl 3 by Raman spectroscopy and observed similar behavior as in the case of the bulk material, including the signatures of possible fractionalized excitations. In complementary experiments, we investigated the electrical charge transport properties of individual α-RuCl 3 nanoflakes in the temperature range between 120 and 290 K. The observed temperature-dependent electrical resistivity is consistent with variable range hopping behavior and exhibits a transition at about 180 K, close to the onset temperature observed in our Raman measurements. In conjunction with the established relation between structure and magnetism in the bulk, we interpret this transition to coincide with the emergence of fractionalized excitations due to the Kitaev interactions in the nanoflakes. Compared to the bulk samples, the transition temperature of the underlying structural change is larger in the nanoflakes. This difference is tentatively attributed to the dimensionality of the nanoflakes as well as the formation of stacking faults during mechanical exfoliation. The demonstrated devices open up novel perspectives toward manipulating the Kitaev-phase in α-RuCl 3 via electrical means.

Two crystalline modifications of RuO4

International Nuclear Information System (INIS)

Pley, Martin; Wickleder, Mathias S.

2005-01-01

RuO 4 was prepared by oxidation of elemental ruthenium. Two different modifications were obtained and investigated by X-ray single crystal diffraction. RuO 4 -I has cubic symmetry (P4; - 3n,Z=8,a=8.509(1)A), and two independent tetrahedral molecules are present in the unit cell. Within the standard uncertainties in both molecules the distances Ru-O are 1.695A. The second modification, RuO 4 -II, is monoclinic (C2/c,Z=4,a=9.302(4)A,b=4.3967(10)A,c=8.454(4)A,β=116.82(3) o ) and isotypic with OsO 4 . There is one independent molecule in the unit cell, which shows distances Ru-O of 1.697 and 1.701A, respectively

Mechanistic study of oxidation of d-arabinose by N-bromophthalimide in presence of micro-amount of chloro-complex of Ru(III as a homogeneous catalyst

Directory of Open Access Journals (Sweden)

Neerja Sachdev

2017-11-01

Full Text Available The kinetics and mechanism of Ru(III-catalyzed oxidation of d-arabinose (d-Ara by N-bromophthalimide (NBP in a acidic medium were investigated using titrimetric method for the redox reaction in the temperature range of 303–323 K. The reaction was first order with respect to [NBP] and [Ru(III]. In both cases, the reaction followed identical kinetics with positive fractional order for [d-Ara] and [H+]. Negative effect with increase in [Cl−], [CH3COOH] and [acetonitrile] could also be observed. Erythronic acid and formic acid were identified as main oxidation products of the reaction. Reduced product of the oxidant i.e. phthalimide did not show significant effect on oxidation rate. Various activation parameters have also been evaluated. Finally a plausible mechanism has been proposed from the kinetic results, reaction stoichiometry and product analysis.

Spectroscopy of {sup 96}Ru and {sup 98}Ru: structures of varied character at N {>=} 52

Energy Technology Data Exchange (ETDEWEB)

Reviol, W; Garg, U; Aprahamian, A; Davis, B F; Herr, M C; Naguleswaran, S; Walpe, J C; Ye, D [Notre Dame Univ., IN (United States); Ahmad, I; Carpenter, M P; Janssens, R V.F.; Khoo, T L; Lauritsen, T; Liang, Y [Argonne National Lab., IL (United States)

1992-08-01

The authors have investigated the onset of deformation at N {>=} 52 by performing high-spin gamma spectroscopy of {sup 96-98}Ru using the {sup 65}Cu({sup 36}S,pxn) reaction with the Argonne-Notre Dame {gamma}-ray facility. From the coincidence data associated with high multiplicity (k {>=} 8) events, they have established two main band structures in {sup 96-98}Ru which extend the previously-known level schemes significantly (up to > 20 {Dirac_h}). In {sup 96}Ru, one of the newly observed structures consists of five rotation-like E2 transitions and feeds into the known 9{sup (-)} state; the other structure bypasses the first one, and based on the observed level-spacings, is tentatively described as vibration-like. A rotational-like structure above a spin of 8 {Dirac_h}, along with a parallel vibration-like structure, has been observed in {sup 98}Ru as well. The data also contain some evidence for a weak sequence of dipole (presumably M1) transitions in {sup 96}Ru. This structure might be similar to the high-K oblate bands recently observed in {sup 119-123}I and {sup 198-20P}b. 9 refs., 3 figs.

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

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.

On the Origin of Charge Order in RuCl3

Science.gov (United States)

Berlijn, Tom

RuCl3 has been proposed to be a spin-orbit assisted Mott insulator close to the Kitaev-spin-liquid ground state, an exotic state of matter that could protect information in quantum computers. Recent STM experiments [M. Ziatdinov et al, Nature Communications (in press)] however, show the presence of a puzzling short-range charge order in this quasi two dimensional material. Understanding the nature of this charge order may provide a pathway towards tuning RuCl3 into the Kitaev-spin-liquid ground state. Based on first principles calculations I investigate the possibility that the observed charge order is caused by a combination of short-range magnetic correlations and strong spin-orbit coupling. From a general perspective such a mechanism could offer the exciting possibility of probing local magnetic correlations with standard STM. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

Comparative Theoretical Study of the Ring-Opening Polymerization of Caprolactam vs Caprolactone Using QM/MM Methods

Energy Technology Data Exchange (ETDEWEB)

Elsasser, Brigitta M.; Schoenen, Iris; Fels, Gregor

2013-06-07

Candida antarctica lipase B (CALB) efficiently catalyzes the ring-opening polymerization of lactones to high molecular weight products in good yield. In contrast, an efficient enzymatic synthesis of polyamides has so far not been described in the literature. This obvious difference in enzyme catalysis is the subject of our comparative study of the initial steps of a CALB catalyzed ring-opening polymerization of ε- caprolactone and ε-caprolactam. We have applied docking tools to generate the reactant state complex and performed quantum mechanical/molecular mechanical (QM/MM) calculations at the density functional theory (DFT) PBE0 level of theory to simulate the acylation of Ser105 by the lactone and the lactam, respectively, via the corresponding first tetrahedral intermediates. We could identify a decisive difference in the accessibility of the two substrates in the ring-opening to the respective acyl enzyme complex as the attack of ε-caprolactam is hindered because of an energetically disfavored proton transfer during this part of the catalytic reaction while ε-caprolactone is perfectly processed along the widely accepted pathway using the catalytic triade of Ser105, His224, and Asp187. Since the generation of an acylated Ser105 species is the crucial step of the polymerization procedure, our results give an explanation for the unsatisfactory enzymatic polyamide formation and opens up new possibilities for targeted rational catalyst redesign in hope of an experimentally useful CALB catalyzed polyamide synthesis.

Atomic layer deposition of Ru thin film using N{sub 2}/H{sub 2} plasma as a reactant

Energy Technology Data Exchange (ETDEWEB)

Hong, Tae Eun [Busan Center, Korea Basic Science Institute, 1275 Jisadong, Gangseogu, Busan, 618-230 (Korea, Republic of); Mun, Ki-Yeung; Choi, Sang-Kyung; Park, Ji-Yoon [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Kim, Soo-Hyun, E-mail: soohyun@ynu.ac.kr [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Cheon, Taehoon [Center for Core Research Facilities, Daegu Gyeongbuk Institute of Science and Technology, Sang-ri, Hyeonpung-myeon, Dalseong-gun, Daegu (Korea, Republic of); Kim, Woo Kyoung [School of Chemical Engineering, Yeungnam University, 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Lim, Byoung-Yong; Kim, Sunjung [School of Materials Science and Engineering, University of Ulsan, Mugeo-dong, Nam-go, Ulsan, 680-749 (Korea, Republic of)

2012-07-31

Ruthenium (Ru) thin films were grown by atomic layer deposition using IMBCHRu [({eta}6-1-Isopropyl-4-MethylBenzene)({eta}4-CycloHexa-1,3-diene)Ruthenium(0)] as a precursor and a nitrogen-hydrogen mixture (N{sub 2}/H{sub 2}) plasma as a reactant, at the substrate temperature of 270 Degree-Sign C. In the wide range of the ratios of N{sub 2} and total gas flow rates (fN{sub 2}/N{sub 2} + H{sub 2}) from 0.12 to 0.70, pure Ru films with negligible nitrogen incorporation of 0.5 at.% were obtained, with resistivities ranging from {approx} 20 to {approx} 30 {mu} Ohm-Sign cm. A growth rate of 0.057 nm/cycle and negligible incubation cycle for the growth on SiO{sub 2} was observed, indicating the fast nucleation of Ru. The Ru films formed polycrystalline and columnar grain structures with a hexagonal-close-packed phase. Its resistivity was dependent on the crystallinity, which could be controlled by varying the deposition parameters such as plasma power and pulsing time. Cu was electroplated on a 10-nm-thick Ru film. Interestingly, it was found that the nitrogen could be incorporated into Ru at a higher reactant gas ratio of 0.86. The N-incorporated Ru film ({approx} 20 at.% of N) formed a nanocrystalline and non-columnar grain structure with the resistivity of {approx} 340 {mu} Ohm-Sign cm. - Highlights: Black-Right-Pointing-Pointer Atomic layer deposition (ALD) of Ru and N-incorporated Ru film using N{sub 2}/H{sub 2} plasma. Black-Right-Pointing-Pointer The growth rate of 0.057 nm/cycle and negligible incubation cycle. Black-Right-Pointing-Pointer A low resistivity of Ru ({approx} 16.5 {mu} Ohm-Sign cm) at the deposition temperature of 270 Degree-Sign C. Black-Right-Pointing-Pointer Electroplating of Cu on a 10-nm-thick ALD-Ru film.

Synthesis of Ru/PDMS nano-composites via supercritial deposition

Energy Technology Data Exchange (ETDEWEB)

Ge, Minglan [Dept. of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617 (China); Bozbag, Selmi E. [Dept. of Chemical and Biological Engineering, Koç University, 34450 Sariyer, Istanbul (Turkey); Ayala, Christian J.; Aindow, Mark [Department of Materials Science and Engineering, Institute of Materials Science, University of Connecticut, Storrs, CT 06269 (United States); Erkey, Can, E-mail: cerkey@ku.edu.tr [Dept. of Chemical and Biological Engineering, Koç University, 34450 Sariyer, Istanbul (Turkey); Koç University TÜPRAŞ Energy Center (KUTEM), Koç University, 34450 Sariyer, Istanbul (Turkey)

2016-09-01

Nanomaterials consisting of Ru nanoparticles dispersed in polydimethylsiloxane films were synthesized by supercritical deposition. The films were impregnated with the organometallic precursor bis(2,2,6,6-tetramethyl-3,5-heptanedionato) (1,5-cyclooctadiene) ruthenium (II) under thermodynamic control in the presence of supercritical carbon dioxide (scCO{sub 2}) at 40 °C and 10.34 MPa. The precursor molecules were then converted to metallic Ru by thermal treatment in flowing N{sub 2} at ambient pressure, resulting in well-dispersed nanoparticles with diameters of ≈2 nm. - Highlights: • PDMS-Ru nanoparticle composites were prepared using supercritical deposition. • PDMS-Ru nanoparticle composites were prepared without using an immobilization agent. • PDMS films were impregnated with Ru(cod)(tmhd){sub 2} in supercritical CO{sub 2}. • The impregnated Ru(cod)(tmhd){sub 2} was then reduced to metallic Ru in flowing N{sub 2}. • The resulting Ru nanoparticles were well-dispersed and had diameters of ≈2 nm.

Carbon monoxide oxidation on bimetallic Ru/Au(111 surfaces

Directory of Open Access Journals (Sweden)

ROLF-JÜRGEN BEHM

2001-02-01

Full Text Available The electrochemical deposition of Ru on Au(111 was performed in 0.5 M H2SO4+10-4 M RuCl3 . The obtained bimetallic Ru/Au(111 surfaces were character-ised by cyclic voltammetry and in situ STM in 0.5 MH2SO4. The Ru deposit consists of nanoscale islands, which merge with increasing coverage. Two different types of bimetallic Ru/Au(111 surfaces with respect to the distribution of Ru islands over the Au(111 substrate surface were obtained. When the deposition was performed at potentials more positive than the range of Au(111 reconstruction, homogeneous nucleation occured resulting in a random distribution of Ru islands. When the deposition was performed on reconstructed Au(111 at low overpotentials, selective nucleation occured resulting in the replication of the Au(111 reconstruction. Only at higher deposition overpotentials, can multilayer deposits be formed, which exhibit a very rough surface morphology. The electrocatalytic activity of such structurally well defined Ru/Au(111 bimetallic surfaces was studied towards CO oxidation with the Ru coverage ranging from submonolayer to several monolayer. COstripping commences at about 0.2 Vand occurs over a broad potential range. The observed influence of the Ru structure on the CO stripping voltammetry is explained by local variations in the COadsorption energy, caused by differences in the local Ru structure and by effects induced by the Au(111 substrate.

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.

A model system for carbohydrates interactions on single-crystalline Ru surfaces

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Thanh Nam

2015-07-01

In this thesis, I present a model system for carbohydrate interactions with single-crystalline Ru surfaces. Geometric and electronic properties of copper phthalocyanine (CuPc) on top of graphene on hexagonal Ru(0001), rectangular Ru(10 anti 10) and vicinal Ru(1,1, anti 2,10) surfaces have been studied. First, the Fermi surfaces and band structures of the three Ru surfaces were investigated by high-resolution angle-resolved photoemission spectroscopy. The experimental data and theoretical calculations allow to derive detailed information about the momentum-resolved electronic structure. The results can be used as a reference to understand the chemical and catalytic properties of Ru surfaces. Second, graphene layers were prepared on the three different Ru surfaces. Using low-energy electron diffraction and scanning tunneling microscopy, it was found that graphene can be grown in well-ordered structures on all three surfaces, hexagonal Ru(0001), rectangular Ru(10 anti 10) and vicinal Ru(1,1, anti 2,10), although they have different surface symmetries. Evidence for a strong interaction between graphene and Ru surfaces is a 1.3-1.7 eV increase in the graphene π-bands binding energy with respect to free-standing graphene sheets. This energy variation is due to the hybridization between the graphene pi bands and the Ru 4d electrons, while the lattice mismatch does not play an important role in the bonding between graphene and Ru surfaces. Finally, the geometric and electronic structures of CuPc on Ru(10 anti 10), graphene/Ru(10 anti 10), and graphene/Ru(0001) have been studied in detail. CuPc molecules can be grown well-ordered on Ru(10 anti 10) but not on Ru(0001). The growth of CuPc on graphene/Ru(10 anti 10) and Ru(0001) is dominated by the Moire pattern of graphene. CuPc molecules form well-ordered structures with rectangular unit cells on graphene/Ru(10 anti 10) and Ru(0001). The distance of adjacent CuPc molecules is 15±0.5 Aa and 13±0.5 Aa on graphene/Ru(0001

Effects of countercations on the structures and redox and spectroscopic properties of diruthenium catecholate complexes with ligand-unsupported Ru-Ru bonds.

Science.gov (United States)

Chang, Ho-Chol; Mochizuki, Katsunori; Kitagawa, Susumu

2005-05-30

The molecular structures and physicochemical properties of diruthenium complexes with ligand-unsupported Ru-Ru bonds, generally formulated as [A2{Ru2(DTBCat)4}] (DTB = 3,5- or 3,6-di-tert-butyl; Cat(2-) = catecholate), were studied in detail by changing the countercations. First, the binding structures of the cations in a family of [{A(DME)n}2{Ru2(3,5-DTBCat)4}] (n = 2 for A+ = Li+ and Na+ and n = 1 for A+ = K+ and Rb+) were systematically examined to reveal the effects of the cations on the molecular structures and electrochemical properties. Second, the complex (n-Bu4N)2[Ru2(3,6-DTBCat)4] with a cation-free structure was synthesized using tetra-n-butylammonium cations. The complex clearly demonstrates first that the ligand-unsupported Ru-Ru bonds are essentially stabilized by the dianionic nature of the catecholate derivatives without any other bridging or supporting species. In contrast, the redox potentials and absorption spectra of the complexes can sensitively respond to the countercations depending upon the polarity of the solvents.

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.

Methanol electro-oxidation on Pt-Ru-P/C and Pt-Ru-P/MWCNT in acidic medium

CSIR Research Space (South Africa)

Modibedi, M

2009-06-01

Full Text Available . The electro-catalytic activity towards methanol oxidation in acidic medium was studied by cyclic voltammetry and linear sweep voltammetry. Pt-Ru-P/MWCNT showed excellent activity compared to that of Pt-Ru-P/C. This may be attributed to the effectiveness...

Magnetic properties of the filled skutterudite-type structure compounds GdRu4P12 and TbRu4P12 synthesized under high pressure

OpenAIRE

Sekine, C; Uchiumi, T; Shirotani, I; Matsuhira, kazuyuki; Sakakibara, T; Goto, T; Yagi, T

2000-01-01

We have succeeded in synthesizing filled skutterudite-type structure compounds GdRu4P12 and TbRu4P12 under high pressure. The magnetic properties of GdRu4P12 and TbRu4P12 have been studied by means of electrical resistivity, magnetic susceptibility, and magnetization measurements. Magnetic experiments suggest that the Gd and Tb ions in the compounds have trivalent state. The compound GdRu4P12 displays features that suggest the occurrence of antiferromagnetic ordering below TN=22 K. In TbRu4P1...

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...

Ru(II)-Catalyzed Oxidative Heck-Type Olefination of Aromatic Carboxylic Acids with Styrenes through Carboxylate-Assisted C-H Bond Activation.

Science.gov (United States)

Dana, Suman; Mandal, Anup; Sahoo, Harekrishna; Mallik, Sumitava; Grandhi, Gowri Sankar; Baidya, Mahiuddin

2018-02-02

A straightforward synthesis of 2-styrylbenzoic acids from aryl carboxylic acids is disclosed through a carboxylate-assisted coupling under Ru(II) catalysis. This protocol is simple and exhibits broad scope with high tolerance of common organic functional groups, providing good to excellent yields of diverse olefinated products. The efficacy of this protocol has been showcased through sequential syntheses of isochromanone, isocoumarin, and formal synthesis of anacardic acid derivative in good yields.

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

Nanoscale decomposition of Nb-Ru-O

Science.gov (United States)

Music, Denis; Geyer, Richard W.; Chen, Yen-Ting

2016-11-01

A correlative theoretical and experimental methodology has been employed to explore the decomposition of amorphous Nb-Ru-O at elevated temperatures. Density functional theory based molecular dynamics simulations reveal that amorphous Nb-Ru-O is structurally modified within 10 ps at 800 K giving rise to an increase in the planar metal - oxygen and metal - metal population and hence formation of large clusters, which signifies atomic segregation. The driving force for this atomic segregation process is 0.5 eV/atom. This is validated by diffraction experiments and transmission electron microscopy of sputter-synthesized Nb-Ru-O thin films. Room temperature samples are amorphous, while at 800 K nanoscale rutile RuO2 grains, self-organized in an amorphous Nb-O matrix, are observed, which is consistent with our theoretical predictions. This amorphous/crystalline interplay may be of importance for next generation of thermoelectric devices.

Classification of domains of closed operators

International Nuclear Information System (INIS)

Lassner, G.; Timmermann, W.

1975-01-01

The structure of domains of determining closed operators in the Hilbert space by means of sequence spaces is investigated. The final classification provides three classes of these domains. Necessary and sufficient conditions of equivalence of these domains are obtained in the form of equivalency of corresponding sequences of natural numbers. Connection with the perturbation theory is mentioned [ru

Reactivity toward alcohols of (Ru/sup IV/ = O/sup 2-/) unit in trans-(RuCl(O)(py)/sub 4/)/sup +/

Energy Technology Data Exchange (ETDEWEB)

Aoyagi, Kimitake; Nagao, Hirotaka; Yukawa, Yasuhiko; Ogura, Mariko; Kuwayama, Akito; Howell, F S; Mukaida, Masao; Kakihana, Hidetake

1986-12-01

The reactivity with alcohol of trans-(RuCl(O)(py)/sub 4/)/sup +/ was investigated. In MeOH, trans-(RuCl(OH)(py)/sub 4/)/sup +/ was confirmed to exist as a precursor in the formation of trans-(RuCl(OMe)(py)/sub 4/)/sup +/. The reaction progress was traced by spectrometrical and /sup 18/O-labelling experiments.

The provenance investigation on ancient chinese Ru porcelains by NAA

International Nuclear Information System (INIS)

Gao Zhengyao; Wang Jie; Chen Songhua

1997-01-01

The 28 samples of glazes and bodies of ancient Chinese Ru porcelains are analyzed by neutron activation. The 36 element contents in each sample are determined. The neutron activation analysis (NAA) data are analyzed by fuzzy cluster. The trend cluster diagram is obtained. The result shows that the ancient Chinese Ru porcelains were most probably from the same raw material source though they were from different time, fired in different kilns and in different colors. The near provenance relation between ancient Jun porcelain and ancient Ru porcelain is preliminarily analyzed. The two modern Ru porcelains approximate to ancient Ru porcelains, one becomes estranged from ancient Ru porcelains. Jingdezhen porcelain is unconcerned with Ru porcelains

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.

Structure and composition of single Pt–Ru electrocatalyst nanoparticles supported on multiwall carbon nanotubes

International Nuclear Information System (INIS)

Paraguay-Delgado, Francisco; Malac, Marek; Alonso-Nuñez, Gabriel

2014-01-01

Individual Pt-Ru nanoparticles (NPs) supported on multiwall carbon nanotubes (MWCNTs) synthesized by microemulsion method were characterized by nano beam diffraction (NBD) and high resolution imaging in transmission electron microscopy (TEM). Comparing the TEM images and NBD to simulations provided insight into particle composition, structure and morphology in three dimensions. In particular, the NBD allowed us to detect various components of the individual NPs that would be difficult to observe otherwise. We find that the NPs contain four different components: Pt–RuO 2 , Pt–Ru, RuO 2 and metallic Pt. Often an individual NP is composed of more than one component. The most frequently encountered external morphology is close to a spherical shape and ∼3.7 nm in diameter. The collective properties of NPs’ assemblies were studied by thermogravimetry, differential thermal analysis and x-ray diffraction. The results allowed us to gain some insight into the relation of the NPs’ structure and composition with their catalytic performance, and revealed the presence of components not detectable by bulk methods. The electrocatalytic properties were evaluated by CO stripping, methanol oxidation and oxygen reduction. Bulk characterization methods miss many properties and structures present in the sample due to low volume fraction and due to overlap of reflections. Single NPs should be analyzed to obtain reliable indication of sample composition. (paper)

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.

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

Directory of Open Access Journals (Sweden)

Jakub Saadi

2016-06-01

Full Text Available Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II back to palladium(0 which is apparently achieved by the present triethylamine.

An investigation of the Pd-Ag-Ru-Gd quaternary system phase diagram

International Nuclear Information System (INIS)

Zhang Kanghou; Xu Yun

2005-01-01

On the basis of the Ag-Pd-Gd, Ag-Ru-Gd and Pd-Ru-Gd ternary systems, the partial phase diagram of Pd-Ag-Ru-Gd (Gd 3 Gd and Ag 51 Gd 14 ; five two-phase regions: Pd(Ag) + (Ru), Pd(Ag) + Ag 51 Gd 14 (Ru) + Ag 51 Gd 14 , Pd(Ag) + Pd 3 Gd and (Ru) + Pd 3 Gd; three three-phase regions: Pd(Ag) + Pd 3 Gd + (Ru), Pd(Ag) + Ag 51 Gd 14 + (Ru) and (Ru) + Ag 51 Gd 14 + Pd 3 Gd; one four-phase region Pd(Ag) + (Ru) + Ag 51 Gd 14 + Pd 3 Gd. No new quaternary intermetallic phase has been found

High-Entropy Alloys in Hexagonal Close-Packed Structure

Science.gov (United States)

Gao, M. C.; Zhang, B.; Guo, S. M.; Qiao, J. W.; Hawk, J. A.

2016-07-01

The microstructures and properties of high-entropy alloys (HEAs) based on the face-centered cubic and body-centered cubic structures have been studied extensively in the literature, but reports on HEAs in the hexagonal close-packed (HCP) structure are very limited. Using an efficient strategy in combining phase diagram inspection, CALPHAD modeling, and ab initio molecular dynamics simulations, a variety of new compositions are suggested that may hold great potentials in forming single-phase HCP HEAs that comprise rare earth elements and transition metals, respectively. Experimental verification was carried out on CoFeReRu and CoReRuV using X-ray diffraction, scanning electron microscopy, and energy dispersion spectroscopy.

Standard enthalpies of formation of selected Ru{sub 2}YZ Heusler compounds

Energy Technology Data Exchange (ETDEWEB)

Yin, Ming, E-mail: myin1@hawk.iit.edu; Nash, Philip

2015-06-15

Highlights: • Standard enthalpies of formation of Ru{sub 2}YZ were measured using a drop calorimeter. • Result of L2{sub 1} structured compounds agrees with first principles data. • Lattice parameters and related phase relationships were consistent with literature data. • Ru{sub 2}HfSn, Ru{sub 2}TiSn, Ru{sub 2}VGa, Ru{sub 2}VSi, Ru{sub 2}VSn of L2{sub 1} structure were reported for the first time. - Abstract: The standard enthalpies of formation of selected ternary Ru-based Heusler compounds Ru{sub 2}YZ (Y = Fe, Hf, Mn, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) were measured using high temperature direct reaction calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the Heusler compounds are, Ru{sub 2}FeGe (−19.7 ± 3.3); Ru{sub 2}HfSn (−24.9 ± 3.6); Ru{sub 2}MnSi (−46.0 ± 2.6); Ru{sub 2}MnGe (−29.7 ± 1.0); Ru{sub 2}MnSn (−20.6 ± 2.4); Ru{sub 2}TiSi (−94.9 ± 4.0); Ru{sub 2}TiGe (−79.1 ± 3.2); Ru{sub 2}TiSn (−60.6 ± 1.8); Ru{sub 2}VSi (−55.9 ± 1.7);for the B2-structured compounds, Ru{sub 2}FeSi (−28.5 ± 0.8); Ru{sub 2}HfAl (−70.8 ± 1.9); Ru{sub 2}MnAl (−32.3 ± 1.9); Ru{sub 2}MnGa (−25.3 ± 3.0); Ru{sub 2}TiAl (−62.7 ± 3.5); Ru{sub 2}VAl (−30.9 ± 1.6); Ru{sub 2}ZrAl (−64.5 ± 1.5). Values were compared with those from published first principles calculations and the OQMD (Open Quantum Materials Database). Lattice parameters of these compounds were determined using X-ray diffraction analysis (XRD). Microstructures were identified using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS)

Gold-Catalyzed Cyclization of Furan-Ynes bearing a Propargyl Carbonate Group: Intramolecular Diels-Alder Reaction with In Situ Generated Allenes.

Science.gov (United States)

Sun, Ning; Xie, Xin; Chen, Haoyi; Liu, Yuanhong

2016-09-26

Gold-catalyzed cyclization of various furan-ynes with a propargyl carbonate or ester moiety results in the formation of a series of polycyclic aromatic ring systems. The reactions can be rationalized through a tandem gold-catalyzed 3,3-rearrangement of the propargyl carboxylate moiety in furan-yne substrates to form an allenic intermediate, which is followed by an intramolecular Diels-Alder reaction of furan and subsequent ring-opening of the oxa-bridged cycloadduct. It was found that the steric and electronic properties of phosphine ligands on the gold catalyst had a significant impact on the reaction outcome. In the case of 1,5-furan-yne, the cleavage of the oxa-bridge in the cycloadduct with concomitant 1,2-migration of the R(1) group occurs to furnish anthracen-1(2H)-ones bearing a quaternary carbon center. For 1,4-furan-yne, a facile aromatization of the cycloadduct takes place to give 9-oxygenated anthracene derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A detailed kinetic study of the direct ring opening of cyclohexane and methylcyclohexane over monofunctional Ir/Al{sub 2}O{sub 3} catalysts

Energy Technology Data Exchange (ETDEWEB)

Shi, Hui; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

2011-07-01

The present study analyses a series of Al{sub 2}O{sub 3}-supported iridium catalysts with different pretreatments and addresses the kinetic features and structural requirements of direct ring opening of cyclohexane and methylcyclohexane catalyzed by Ir in absence of acid-catalyzed ring contraction. Mild reaction conditions and high H{sub 2}/hydrocarbon ratios (200-1000) were used to improve accuracy of kinetic measurements and to negate deactivation. Isomerization and dehydrogenation pathways were suppressed to low extents (1-5%) over the weakly acidic catalysts under the reaction conditions applied. Three main observations are shown: 1) initial selectivity to ring opening products (ROPs) increases with iridium dispersion; 2) optimal H{sub 2} pressures differ not only between primary and secondary products, but also among ROPs and fragments; 3) the air-calcination step before catalyst reduction imposes a significant impact on both activity and product distribution. (orig.)

Generator separation of 103Ru//sup 103m/Rh

International Nuclear Information System (INIS)

Epperson, C.E.

1975-01-01

A generator for producing carrier-free Rh-103m was developed using a liquid extraction technique. Initially, Ru-103 chloride was converted to the sulfate by moderate fuming for 80 minutes in 1:1 sulfuric acid. The Ru-103 was then brought to its highest oxidation state with 0.2 N ceric sulfate. Ru-103 tetroxide was removed from an aqueous equilibrium solution of Ru-103/Rh-103m by three one-minute extractions into CCl 4 . The Rh-103m daughter was not extracted under these conditions. Yields of Rh-103m exceeded 90 percent theoretical. The Ru-103 removed by CCl 4 could be recovered by two hours of back-extraction into 2 M sulfuric acid containing 5 mg of sodium sulfite. A cyclic extraction system was made possible by employing sulfate media. Equilibrium Ru-103 could be repeatedly extracted and recovered, thereby producing a ''generator'' system for the production of Rh-103m. Ru-103 chloride can be converted to the sulfate and then stored for at least 38 days prior to extraction. By performing the fuming step whenever convenient, the time required to perform an extraction separation was reduced to 15 minutes. Prior treatment of glassware surfaces with dilute sulfuric acid prevented Ru-103 glass adsorption losses and made glassware much easier to decontaminate. Off-the-shelf reagent-grade CCl 4 could be used without further purification. Efforts to separate Rh-103m from Ru-103 by chromatography techniques were unsuccessful

PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: brandalise@usp.br, E-mail: mmtusi@usp.br, E-mail: rmpiasen@ipen.br, E-mail: ovcorrea@ipen.br, E-mail: mlinardi@ipen.br, E-mail: espinace@ipen.br, E-mail: aolivei@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2009-07-01

PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H{sub 2}PtCl{sub 6.6}H{sub 2}O, RuCl{sub 3.x}H{sub 2}O and Bi(NO{sub 3}){sub 3.5}H{sub 2}O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

International Nuclear Information System (INIS)

Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir

2009-01-01

PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H 2 PtCl 6.6 H 2 O, RuCl 3.x H 2 O and Bi(NO 3 ) 3.5 H 2 O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

High-Density Stacked Ru Nanocrystals for Nonvolatile Memory Application

International Nuclear Information System (INIS)

Ping, Mao; Zhi-Gang, Zhang; Li-Yang, Pan; Jun, Xu; Pei-Yi, Chen

2009-01-01

Stacked ruthenium (Ru) nanocrystals (NCs) are formed by rapid thermal annealing for the whole gate stacks and embedded in memory structure, which is compatible with conventional CMOS technology. Ru NCs with high density (3 × 10 12 cm −2 ), small size (2–4 nm) and good uniformity both in aerial distribution and morphology are formed. Attributed to the higher surface trap density, a memory window of 5.2 V is obtained with stacked Ru NCs in comparison to that of 3.5 V with single-layer samples. The stacked Ru NCs device also exhibits much better retention performance because of Coulomb blockade and vertical uniformity between stacked Ru NCs

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

Semiconductor-metal transition of Se in Ru-Se Catalyst Nanoparticles

Science.gov (United States)

Babu, P. K.; Lewera, Adam; Oldfield, Eric; Wieckowski, Andrzej

2009-03-01

Ru-Se composite nanoparticles are promising catalysts for the oxygen reduction reaction (ORR) in fuel cells. Though the role of Se in enhancing the chemical stability of Ru nanoparticles is well established, the microscopic nature of Ru-Se interaction was not clearly understood. We carried out a combined investigation of ^77Se NMR and XPS on Ru-Se nanoparticles and our results indicate that Se, a semiconductor in elemental form, becomes metallic when interacting with Ru. ^77Se spin-lattice relaxation rates are found to be proportional to T, the well-known Korringa behavior characteristic of metals. The NMR results are supported by the XPS binding energy shifts which suggest that a possible Ru->Se charge transfer could be responsible for the semiconductor->metal transition of Se which also makes Ru less susceptible to oxidation during ORR.

Electron correlation in CaRuO3 and SrRuO3

International Nuclear Information System (INIS)

Singh, Ravi Shankar; Maiti, Kalobaran

2005-01-01

We investigate the role of electron correlation in the electronic structure of 4d transition-metal oxides CaRuO 3 and SrRuO 3 . The photoemission spectra collected at different surface sensitivities reveal qualitatively different surface and bulk electronic structures in these systems. Extracted bulk spectra could be simulated using first principle approaches consistently with their thermodynamic parameters within the same model. The estimated electron correlation strength (U/W ∼ 0.2) is significantly weak as expected in 4d systems and resolves the long-standing issue that arose due to the prediction of large U/W similar to 3d systems. (author)

Biodistribution of Ru-97-labeled DTPA, DMSA and transferrin

International Nuclear Information System (INIS)

Som, P.; Oster, Z.H.; Fairchild, R.G.; Atkins, H.L.; Brill, A.B.; Gil, M.C.; Srivastava, S.C.; Meinken, G.E.; Goldman, A.G.; Richards, P.

1980-01-01

Ruthenium-97 is being produced at the Brookhaven Linac Isotope Producer (BLIP). The favorable physical properties of Ru-97 and chemical reactivity of ruthenium offer a potential for using this isotope to label compounds useful for delayed scanning. Diethylenetriamine pentaacetic acid (DTPA), 2,3-Dimercaptosuccinic acid (DMSA), and Transferrin (TF) were labeled with Ru-97-chloride. Ru-97-DTPA and In-111-DTPA, injected intravenously, showed similar organ distribution, kinetics, and more than 80% excretion by 0.5 h. Ru-97-DTPA and In-111-DTPA injected into the cisterna magna of dogs showed similar kinetics in brain, blood, and urinary bladder. The energy deposited by 1 mCi In-111-DTPA is twice that from 1 mCi Ru-97-DTPA. High quality camera images of the CSF space in the dog were obtained with both isotopes. Ru-97-DMSA was prepared with and without the addition of SnCl 2 .2H 2 O. Tin-free DMSA was rapidly excreted via the kidneys, whereas for maximum cortical deposition, the tin-containing preparation was superior. This compound is suitable for delayed imaging of both normal and impaired kidneys. Tissue distribution studies were performed in abscess-bearing rats with Ru-97-transferrin. Although blood levels were higher than with Ga-67-citrate, the abscess had twice as much Ru-97-TF as Ga-67-citrate and the Ru-97 muscle activity was one-third that of Ga-67. Imaging of abscess-bearing rabbits with Ru-97-TF visualized the abscesses as early as 1/2 hr after injection. Since the initial images visualize the abscess so clearly and since the TF portion of the compound binds to the abscess, Tc-99m-TF is being studied for the same purpose. Ru-97-labeled compounds are a promising replacement for In-111 and possibly also for Ga-67 compounds with the advantages of lower radiation dose and high quality image

Sideward flow of K+ in Ru+Ru and Ni+Ni reactions sat SIS energies

International Nuclear Information System (INIS)

Crochet, P.; Herrmann, N.; Wisniewski, K.

2000-01-01

Experimental data on K + and proton sideward flow measured with the FOPI detector at SIS/GSI in the reactions Ru+Ru at 1.69 A GeV and Ni+Ni at 1.93 A GeV are presented. The K + sideward flow is found to be anti-correlated (correlated) with the one of protons at low (high) transverse momenta. When compared to the predictions of a transport model, the data favour the existence of an in-medium repulsive K + -nucleon potential. (author)

Between Localization and Delocalization: Ru(cod)2+ Units in the Zintl Clusters [Bi9 {Ru(cod)}2 ]3- and [Tl2 Bi6 {Ru(cod)}]2.

Science.gov (United States)

Lichtenberger, Niels; Spang, Nils; Eichhöfer, Andreas; Dehnen, Stefanie

2017-10-16

Reactions of [K(crypt-222)] 2 (TlBi 3 )⋅0.5 en (1 b) with [Ru(cod)(H 2 CC(Me)CH 2 ) 2 ] (A) in 1,2-diaminoethane (en) led to the formation of two compounds with new bismuth-rich cluster anions, [K(crypt-222)] 3 [Bi 9 {Ru(cod)} 2 ]⋅1.5 en (2) and [K(crypt-222)] 2 [Tl 2 Bi 6 {Ru(cod)}]⋅2 tol (3), alongside the salt of a binary nido cluster, [K(crypt-222)] 3 (Tl 4 Bi 5 )⋅2 en (4). The anions in 2 and 3 are two further examples of rare heterometallic clusters containing Ru atoms. As one cod ligand is retained on each Ru atom in both clusters, the anions may be viewed as intermediates on the way towards larger, ligand-free intermetalloid clusters. Quantum-chemical studies provided insight into the bonding situation in these clusters. According to these studies, the anion of 2 features both electron-precise and electron-deficient parts. Electrospray ionization mass spectrometry analysis indicated that the clusters undergo stepwise fragmentation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unconventional superconductivity in Sr{sub 2}RuO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Liu, Ying [Department of Physics and Materials Research Institute, Pennsylvania State University, University Park, PA 16802 (United States); Key Laboratory of Artificial Structures and Quantum Control (Ministry of Education), Department of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai 200240 (China); Collaborative Innovation Center of Advanced Microstructures, Nanjing 210093 (China); Mao, Zhi-Qiang [Department of Physics and Engineering Physics, Tulane University, New Orleans, LA 70118 (United States)

2015-07-15

Highlights: • Constraints on and experimental support to unconventional superconductivity in Sr{sub 2}RuO{sub 4}. • Phase-sensitive determination of the pairing symmetry in Sr{sub 2}RuO{sub 4}. • Response of superconductivity to mechanical perturbations. • Superconductivity in non-bulk Sr{sub 2}RuO{sub 4}. • Unresolved issues and outlook in Sr{sub 2}RuO{sub 4} research. - Abstract: Sr{sub 2}RuO{sub 4}, featuring a layered perovskite crystalline and quasi-two-dimensional electronic structure, was first synthesized in 1959. Unconventional, p-wave pairing was predicted for Sr{sub 2}RuO{sub 4} by Rice and Sigrist and Baskaran shortly after superconductivity in this material was discovered in 1994. Experimental evidence for unconventional superconductivity in Sr{sub 2}RuO{sub 4} has been accumulating in the past two decades and reviewed previously. In this article, we will first discuss constraints on the pairing symmetry of superconductivity in Sr{sub 2}RuO{sub 4} and summarize experimental evidence supporting the unconventional pairing symmetry in this material. We will then present several aspects of the experimental determination of the unconventional superconductivity in Sr{sub 2}RuO{sub 4} in some detail. In particular, we will discuss the phase-sensitive measurements that have played an important role in the determination of the pairing symmetry in Sr{sub 2}RuO{sub 4}. The responses of superconductivity to the mechanical perturbations and their implications on the mechanism of superconductivity will be discussed. A brief survey of various non-bulk Sr{sub 2}RuO{sub 4} will also be included to illustrate the many unusual features resulted from the unconventional nature of superconductivity in this material system. Finally, we will discuss some outstanding unresolved issues on Sr{sub 2}RuO{sub 4} and provide an outlook of the future work on Sr{sub 2}RuO{sub 4}.

Improvements of electrocatalytic activity of PtRu nanoparticles on multi-walled carbon nanotubes by a H2 plasma treatment in methanol and formic acid oxidation

International Nuclear Information System (INIS)

Jiang Zhongqing; Jiang Zhongjie

2011-01-01

Graphical abstract: A H 2 plasma, that aims at reducing the fraction of the oxidized species at the outermost perimeter of metal particles, has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, reduced charge transfer resistance, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. Highlights: → A H 2 plasma technique is used to treat the PtRu nanoparticles. → The H 2 plasma treated PtRu/PS-MWCNTs exhibit improved electrocatalytic activity. → The H 2 plasma treated PtRu/PS-MWCNTs have significantly reduced charge transfer resistance. → The H 2 plasma treated PtRu/PS-MWCNTs show the increased stability. → The Pt:Ru atomic ratio of PtRu nanoparticles has a significant effect on the electrochemical activity. - Abstract: A H 2 plasma has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treatment does not change the size and crystalline structure of PtRu nanoparticles, but reduces the fraction of the oxidized species at the outermost perimeter of particles. The electrochemical results show that these plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. The electrocatalytic activities of the plasma treated PtRu/PS-MWCNTs are found to be dependent upon the Pt:Ru atomic ratios of PtRu nanoparticles. The catalysts with a Pt:Ru atomic ratio close to 1:1 show superior properties in the electrooxidation of methanol and formic acid

Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

KAUST Repository

Ladelta, Viko

2016-12-12

A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

KAUST Repository

Ladelta, Viko; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

2016-01-01

A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

Science.gov (United States)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Binders and Solvents on Stability of Ru/RuOx Nanoparticles on ITO Nanocrystals as Li-O2 Battery Cathodes.

Science.gov (United States)

Vankova, Svetoslava; Francia, Carlotta; Amici, Julia; Zeng, Juqin; Bodoardo, Silvia; Penazzi, Nerino; Collins, Gillian; Geaney, Hugh; O'Dwyer, Colm

2017-02-08

Fundamental research on Li-O 2 batteries remains critical, and the nature of the reactions and stability are paramount for realising the promise of the Li-O 2 system. We report that indium tin oxide (ITO) nanocrystals with supported 1-2 nm oxygen evolution reaction (OER) catalyst Ru/RuO x nanoparticles (NPs) demonstrate efficient OER processes, reduce the recharge overpotential of the cell significantly and maintain catalytic activity to promote a consistent cycling discharge potential in Li-O 2 cells even when the ITO support nanocrystals deteriorate from the very first cycle. The Ru/RuO x nanoparticles lower the charge overpotential compared with those for ITO and carbon-only cathodes and have the greatest effect in DMSO electrolytes with a solution-processable F-free carboxymethyl cellulose (CMC) binder (ITO nanocrystalline materials in DMSO provide efficient Li 2 O 2 decomposition from within the cathode during cycling. We demonstrate that the ITO is actually unstable from the first cycle and is modified by chemical etching, but the Ru/RuO x NPs remain effective OER catalysts for Li 2 O 2 during cycling. The CMC binders avoid PVDF-based side-reactions and improve the cyclability. The deterioration of the ITO nanocrystals is mitigated significantly in cathodes with a CMC binder, and the cells show good cycle life. In mixed DMSO-EMITFSI [EMITFSI=1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] ionic liquid electrolytes, the Ru/RuO x /ITO materials in Li-O 2 cells cycle very well and maintain a consistently very low charge overpotential of 0.5-0.8 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Ruthenium-Catalyzed Formal Dehydrative [4 + 2] Cycloaddition of Enamides and Alkynes for the Synthesis of Highly Substituted Pyridines: Reaction Development and Mechanistic Study.

Science.gov (United States)

Wu, Jicheng; Xu, Wenbo; Yu, Zhi-Xiang; Wang, Jian

2015-07-29

Reported herein is a ruthenium-catalyzed formal dehydrative [4 + 2] cycloaddition of enamides and alkynes, representing a mild and economic protocol for the construction of highly substituted pyridines. Notably, the features of broad substrate scope, high efficiency, good functional group tolerance, and excellent regioselectivities were observed for this reaction. Density functional theory (DFT) calculations and experiments have been carried out to understand the mechanism and regiochemistry. DFT calculations suggested that this formal dehydrative [4 + 2] reaction starts with a concerted metalation deprotonation of the enamide by the acetate group in the Ru catalyst, which generates a six-membered ruthenacycle intermediate. Then alkyne inserts into the Ru-C bond of the six-membered ruthenacycle, giving rise to an eight-membered ruthenacycle intermediate. The carbonyl group (which comes originally from the enamide substrate and is coordinated to the Ru center in the eight-membered ruthenacycle intermediate) then inserts into the Ru-C bond to give an intermediate, which produces the final pyridine product through further dehydration. Alkyne insertion step is a regio-determining step and prefers to have the aryl groups of the used alkynes stay away from the catalyst in order to avoid repulsion of aryl group with the enamide moiety in the six-membered ruthenacycle and to keep the conjugation between the aryl group and the triple C-C bond of the alkynes. Consequently, the aryl groups of the used alkynes are in the β-position of the final pyridines, and the present reaction has high regioselectivity.

Desaturation reactions catalyzed by soluble methane monooxygenase.

Science.gov (United States)

Jin, Y; Lipscomb, J D

2001-09-01

Soluble methane monooxygenase (MMO) is shown to be capable of catalyzing desaturation reactions in addition to the usual hydroxylation and epoxidation reactions. Dehydrogenated products are generated from MMO-catalyzed oxidation of certain substrates including ethylbenzene and cyclohexadienes. In the reaction of ethylbenzene, desaturation of ethyl C-H occurred along with the conventional hydroxvlations of ethyl and phenyl C-Hs. As a result, styrene is formed together with ethylphenols and phenylethanols. Similarly, when 1,3- and 1,4-cyclohexadienes were used as substrates, benzene was detected as a product in addition to the corresponding alcohols and epoxides. In all cases, reaction conditions were found to significantly affect the distribution among the different products. This new activity of MMO is postulated to be associated with the chemical properties of the substrates rather than fundamental changes in the nature of the oxygen and C-H activation chemistries. The formation of the desaturated products is rationalized by formation of a substrate cationic intermediate, possibly via a radical precursor. The cationic species is then proposed to partition between recombination (alcohol formation) and elimination (alkene production) pathways. This novel function of MMO indicates close mechanistic kinship between the hydroxylation and desaturation reactions catalyzed by the nonheme diiron clusters.

Fabrication of a CANFLEX-RU designed bundle for power ramp irradiation test in NRU

International Nuclear Information System (INIS)

Cho, Moon Sung

2000-11-01

The BDL-443 CANFLEX-RU bundle AKW was fabricated at Korea Atomic Energy Research Institute (KAERI) for power ramp irradiation testing in NRU reactor. The bundle was fabricated with IDR and ADU fuel pellets in adjacent elements and contains fuel pellets enriched to 1.65 wt% 235 U in the outer and intermediate rings and also contains pellets enriched to 2.00 wt% 235 U in the inner ring. This bundle does not have a center element to allow for insertion on a hanger bar. KAERI produced the IDR pellets with the IDR-source UO 2 powder supplied by BNFL. ADU pellets were fabricated and supplied by AECL. Bundle kits (Zircaloy-4 end plates, end plugs, and sheaths with brazed appendages) manufactured at KAERI earlier in 1996 were used for the fabrication of the bundle. The CANFLEX bundle was fabricated successfully at KAERI according to the QA provisions specified in references and as per relevant KAERI drawings and technical specification. This report covers the fabrication activities performed at KAERI. Fabrication processes performed at AECL will be documented in a separate report

Measurement of the Ru surface content of electrodeposited PtRu electrodes with the electrochemical quartz crystal microbalance: implications for methanol and CO electrooxidation

NARCIS (Netherlands)

Frelink, T.; Visscher, W.; Veen, van J.A.R.

1996-01-01

To obtain the surface content of Ru in rough electrocodeposited PtRu electrodes, the mass change of a Pt electrode during Ru deposition was measured with the electrochemical quartz crystal microbalance (EQCMB). It is shown that there is a correlation between the potential of the surface oxide

Intramolecular electron transfer in cyanide bridged adducts comprising Ru(II)/Ru(III) tetracarboxylate and [Mn(I)(CO)(CN)((t)BuNC)(4)] units.

Science.gov (United States)

Imhof, Wolfgang; Sterzik, Anke; Krieck, Sven; Schwierz, Markus; Hoffeld, Thomas; Spielberg, Eike T; Plass, Winfried; Patmore, Nathan

2010-07-21

Reaction of mixed valence ruthenium tetracarboxylates [Ru(2)(II,III)(R(1)COO)(2)(R(2)COO)(2)Cl] (R(1) = Me, R(2) = 2,4,6-(i)Pr-Ph or R(1) = R(2) = (t)Bu) with two equivalents of the octahedral manganese complex [Mn(I)(CO)(CN)((t)BuNC)(4)] leads to the formation of cyanide bridged heteronuclear coordination compounds of the general formula {[Ru(2)(II,III)(R(1)COO)(2)(R(2)COO)(2)][Mn(I)(CO)(CN)((t)BuNC)(4)](2)}Cl. In solution an intramolecular electron transfer from manganese towards the multiply bonded Ru(2) core occurs that is verified by EPR and IR spectroscopy, magnetic measurements and DFT calculations. Nevertheless, disproportionation of an initially formed {Mn(I)-Ru(2)(II,III)-Mn(I)}(+) adduct into {Mn(II)-Ru(2)(II,III)-Mn(I)}(2+) and {Mn(I)-Ru(2)(II,II)-Mn(I)} species cannot be completely ruled out.

Structural, optical and magnetic characterization of Ru doped ZnO nanorods

International Nuclear Information System (INIS)

Kumar, Sanjeev; Kaur, Palvinder; Chen, C.L.; Thangavel, R.; Dong, C.L.; Ho, Y.K.; Lee, J.F.; Chan, T.S.; Chen, T.K.; Mok, B.H.; Rao, S.M.; Wu, M.K.

2014-01-01

Graphical abstract: Ruthenium (Ru = 0%, 1% and 2%) doped nano-crystalline zinc oxide (ZnO) nanorods were synthesized by using well-known sol–gel technique. X-ray diffraction (XRD) results show that Ru (0%, 1% and 2%) doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). Williamson and Hall plot reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain in ZnO host matrix. Photoluminescence (PL) and Raman studies of Ru doped ZnO nanorods show the formation of singly ionized oxygen vacancies which may account for the observed room temperature ferromagnetism (RTFM) in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms in the host lattice and maintain the crystal symmetry with slightly lattice distortion. Highlights: • Ru doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). • PL and Raman studies show the formation of singly ionized oxygen vacancies in 2% Ru doped ZnO. • XAS reveals that Ru replace the Zn atoms in the host lattice with slightly lattice distortion. • Doping of Ru in ZnO nanostructures gives rise to RTFM ordering. -- Abstract: Ruthenium (Ru = 0%, 1% and 2%) doped nano-crystalline zinc oxide (ZnO) nanorods were synthesized by using well-known sol–gel technique. X-ray diffraction (XRD) results show that Ru (0%, 1% and 2%) doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). Williamson and Hall plot reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain in ZnO host matrix. Photoluminescence (PL) and Raman studies of Ru doped ZnO nanorods show the formation of singly ionized oxygen vacancies which may account for the observed room temperature ferromagnetism (RTFM) in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms in the host lattice and maintain the crystal symmetry with slightly lattice

Water Induced Surface Reconstruction of the Oxygen (2x1) covered Ru(0001)

Energy Technology Data Exchange (ETDEWEB)

Maier, Sabine; Cabrera-Sanfelix, Pepa; Stass, Ingeborg; Sanchez-Portal, Daniel; Arnau, Andres; Salmeron, Miquel

2010-08-06

Low temperature scanning tunneling microscopy (STM) and density functional theory (DFT) were used to study the adsorption of water on a Ru(0001) surface covered with half monolayer of oxygen. The oxygen atoms occupy hcp sites in an ordered structure with (2x1) periodicity. DFT predicts that water is weakly bound to the unmodified surface, 86 meV compared to the ~;;200 meV water-water H-bond. Instead, we found that water adsorption causes a shift of half of the oxygen atoms from hcp sites to fcc sites, creating a honeycomb structure where water molecules bind strongly to the exposed Ru atoms. The energy cost of reconstructing the oxygen overlayer, around 230 meV per displaced oxygen atom, is more than compensated by the larger adsorption energy of water on the newly exposed Ru atoms. Water forms hydrogen bonds with the fcc O atoms in a (4x2) superstructure due to alternating orientations of the molecules. Heating to 185 K results in the complete desorption of the water layer, leaving behind the oxygen honeycomb structure, which is metastable relative to the original (2x1). This stable structure is not recovered until after heating to temperatures close to 260K.

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

Influence of hydroxylamine conformation on stereocontrol in Pd-catalyzed isoxazolidine-forming reactions.

Science.gov (United States)

Lemen, Georgia S; Giampietro, Natalie C; Hay, Michael B; Wolfe, John P

2009-03-20

Palladium-catalyzed carboamination reactions between N-Boc-O-(but-3-enyl)hydroxylamine derivatives and aryl or alkenyl bromides afford cis-3,5- and trans-4,5-disubstituted isoxazolidines in good yield with up to >20:1 dr. The diastereoselectivity observed in the formation of cis-3,5-disubstituted isoxazolidines is superior to selectivities typically obtained in other transformations, such as 1,3-dipolar cycloaddition reactions, that provide these products. In addition, the stereocontrol in the C-N bond-forming Pd-catalyzed carboamination reactions of N-Boc-O-(but-3-enyl)hydroxylamines is significantly higher than that of related C-O bond-forming carboetherification reactions of N-benzyl-N-(but-3-enyl)hydroxylamine derivatives. This is likely due to a stereoelectronic preference for cyclization via transition states in which the Boc group is placed in a perpendicular orientation relative to the plane of the developing ring, which derives from the conformational equilibria of substituted hydroxylamines.

Electrochemical, spectroscopic, and photophysical properties of structurally diverse polyazine-bridged Ru(II),Pt(II) and Os(II),Ru(II),Pt(II) supramolecular motifs.

Science.gov (United States)

Knoll, Jessica D; Arachchige, Shamindri M; Wang, Guangbin; Rangan, Krishnan; Miao, Ran; Higgins, Samantha L H; Okyere, Benjamin; Zhao, Meihua; Croasdale, Paul; Magruder, Katherine; Sinclair, Brian; Wall, Candace; Brewer, Karen J

2011-09-19

Five new tetrametallic supramolecules of the motif [{(TL)(2)M(dpp)}(2)Ru(BL)PtCl(2)](6+) and three new trimetallic light absorbers [{(TL)(2)M(dpp)}(2)Ru(BL)](6+) (TL = bpy = 2,2'-bipyridine or phen = 1,10-phenanthroline; M = Ru(II) or Os(II); BL = dpp = 2,3-bis(2-pyridyl)pyrazine, dpq = 2,3-bis(2-pyridyl)quinoxaline, or bpm = 2,2'-bipyrimidine) were synthesized and their redox, spectroscopic, and photophysical properties investigated. The tetrametallic complexes couple a Pt(II)-based reactive metal center to Ru and/or Os light absorbers through two different polyazine BL to provide structural diversity and interesting resultant properties. The redox potential of the M(II/III) couple is modulated by M variation, with the terminal Ru(II/III) occurring at 1.58-1.61 V and terminal Os(II/III) couples at 1.07-1.18 V versus Ag/AgCl. [{(TL)(2)M(dpp)}(2)Ru(BL)](PF(6))(6) display terminal M(dπ)-based highest occupied molecular orbitals (HOMOs) with the dpp(π*)-based lowest unoccupied molecular orbital (LUMO) energy relatively unaffected by the nature of BL. The coupling of Pt to the BL results in orbital inversion with localization of the LUMO on the remote BL in the tetrametallic complexes, providing a lowest energy charge separated (CS) state with an oxidized terminal Ru or Os and spatially separated reduced BL. The complexes [{(TL)(2)M(dpp)}(2)Ru(BL)](6+) and [{(TL)(2)M(dpp)}(2)Ru(BL)PtCl(2)](6+) efficiently absorb light throughout the UV and visible regions with intense metal-to-ligand charge transfer (MLCT) transitions in the visible at about 540 nm (M = Ru) and 560 nm (M = Os) (ε ≈ 33,000-42,000 M(-1) cm(-1)) and direct excitation to the spin-forbidden (3)MLCT excited state in the Os complexes about 720 nm. All the trimetallic and tetrametallic Ru-based supramolecular systems emit from the terminal Ru(dπ)→dpp(π*) (3)MLCT state, λ(max)(em) ≈ 750 nm. The tetrametallic systems display complex excited state dynamics with quenching of the (3)MLCT emission at

Ligand sphere conversions in terminal carbide complexes

DEFF Research Database (Denmark)

Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.

2016-01-01

Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first...... example of a cationic terminal carbide complex, [RuC(Cl)(CH3CN)(PCy3)2]+, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide 13C chemical shift is shown to be accurately reproduced by DFT, which also...... demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction...

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.

Quaternary Pt{sub 2}Ru{sub 1}Fe{sub 1}M{sub 1}/C (M=Ni, Mo, or W) catalysts for methanol electro-oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Jeon, Min Ku; Lee, Ki Rak; Kang, Kweon Ho; Park, Geun Il [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Jeon, Hyung Joon [Kyoto University, Kyoto (Japan); McGinn, Paul J. [University of Notre Dame, Indiana (United States)

2015-02-15

Quaternary Pt{sub 2}Ru{sub 1}Fe{sub 1}M{sub 1}/C (M=Ni, Mo, or W) catalysts were investigated for the methanol electro-oxidation reaction (MOR). Electrocatalytic activities of the quaternary catalysts for CO electro-oxidation were studied via CO stripping experiments, and the Pt{sub 2}Ru{sub 1}Fe{sub 1}Ni{sub 1}/C and Pt{sub 2}Ru{sub 1}Fe{sub 1}W{sub 1}/C catalysts exhibited lowered on-set potential compared to that of a commercial PtRu/C catalyst. MOR activities of the quaternary catalysts were determined by linear sweep voltammetry (LSV) experiments, and the Pt{sub 2}Ru{sub 1}Fe{sub 1}W{sub 1}/C catalyst outperformed the commercial PtRu/C catalyst by 170 and 150% for the mass and specific activities, respectively. X-ray photoelectron spectroscopy (XPS) was employed to analyze surface oxidation states of constituent atoms, and it was identified that the structure of the synthesized catalysts are close to a nano-composite of Pt and constituent metal hydroxides and oxides. In addition, the XPS results suggested that the bi-functional mechanism accounts for the improved performance of the Pt{sub 2}Ru{sub 1}Fe{sub 1}Ni{sub 1}/C and Pt{sub 2}Ru{sub 1} Fe{sub 1}W{sub 1}/C catalysts.

Enhanced interfacial Dzyaloshinskii-Moriya interaction and isolated skyrmions in the inversion-symmetry-broken Ru/Co/W/Ru films

Science.gov (United States)

Samardak, Alexander; Kolesnikov, Alexander; Stebliy, Maksim; Chebotkevich, Ludmila; Sadovnikov, Alexandr; Nikitov, Sergei; Talapatra, Abhishek; Mohanty, Jyoti; Ognev, Alexey

2018-05-01

An enhancement of the spin-orbit effects arising on an interface between a ferromagnet (FM) and a heavy metal (HM) is possible through the strong breaking of the structural inversion symmetry in the layered films. Here, we show that an introduction of an ultrathin W interlayer between Co and Ru in Ru/Co/Ru films enables to preserve perpendicular magnetic anisotropy (PMA) and simultaneously induce a large interfacial Dzyaloshinskii-Moriya interaction (iDMI). The study of the spin-wave propagation in the Damon-Eshbach geometry by Brillouin light scattering spectroscopy reveals the drastic increase in the iDMI value with the increase in W thickness (tW). The maximum iDMI of -3.1 erg/cm2 is observed for tW = 0.24 nm, which is 10 times larger than for the quasi-symmetrical Ru/Co/Ru films. We demonstrate the evidence of the spontaneous field-driven nucleation of isolated skyrmions supported by micromagnetic simulations. Magnetic force microscopy measurements reveal the existence of sub-100-nm skyrmions in the zero magnetic field. The ability to simultaneously control the strength of PMA and iDMI in quasi-symmetrical HM/FM/HM trilayer systems through the interface engineered inversion asymmetry at the nanoscale excites new fundamental and practical interest in ultrathin ferromagnets, which are a potential host for stable magnetic skyrmions.

Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives.

Science.gov (United States)

Larksarp, C; Sellier, O; Alper, H

2001-05-18

The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.

Activity of carbon supported Pt3Ru2 nanocatalyst in CO oxidation

Directory of Open Access Journals (Sweden)

KSENIJA DJ. POPOVIĆ

2009-08-01

Full Text Available The electrocatalytic activity of Pt3Ru2/C nanocatalyst toward the electro-oxidation of bulk CO was examined in acid and alkaline solution at ambient temperature using the thin-film, rotating disk electrode (RDE method. The catalyst was characterized by XRD analysis. The XRD pattern revealed that the Pt3Ru2/C catalyst consisted of two structures, i.e., Pt–Ru-fcc and Ru-hcp (a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. Electrocatalytic activities were measured by applying potentiodynamic and steady state techniques. The oxidation of CO on the Pt3Ru2/C catalyst was influenced by pH and anions from the supporting electrolytes. The Pt3Ru2/C was more active in alkaline than in acid solution, as well as in perchloric than in sulfuric acid. Comparison of CO oxidation on Pt3Ru2/C and Pt/C revealed that the Pt3Ru2/C was more active than Pt/C in acid solution, while both catalysts had a similar activity in alkaline solution.

Single hole spectroscopic strength in 98Ru through the 99Ru(d,t) reaction

International Nuclear Information System (INIS)

Rodrigues, M.R.D.; Borello-Lewin, T.; Horodynski-Matsushigue, L.B.; Duarte, J.L.M.; Rodrigues, C.L.; Barbosa, M.D.L.; Silva, G.B. da; Ukita, G.M.

2002-01-01

The 99 Ru(d,t) 98 Ru reaction was measured for the first time at 16 MeV incident energy with the Sao Paulo Pelletron-Enge-spectrograph facility employing the nuclear emulsion technique. In all, up to 3.5 MeV, 23 levels were detected, eight of them new; angular distributions are presented for all of them. Least squares fits of distorted wave Born approximation one-neutron pickup predictions to the rather well structured experimental angular distributions enabled the determination of l transfers and of the corresponding spectroscopic factors for 19 of these states, some being tentative attributions. Only transfers of l=0, 2, and 4 were observed. Several states were populated through single l transfers. A pure l=2 transfer is associated with the 2 1 + level and with several other states which are considered collective, as well as with the (4 + ) state at 2.277 MeV, which presents the highest spectroscopic strength. Considering five valence neutrons above the N=50 core, only 41% of the spectroscopic strength expected for 99 Ru was detected

RuBee and RFID A confidential summary,May 2009

Institute of Scientific and Technical Information of China (English)

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2009-01-01

The letters"RFID"have become a negative to many of our end-customers,so we have had to distance RuBee from the entire category and discourage any attempt to characterize RuBee as just another RFID technology.We never engage in pilots or trials where RFID is seen as a competing technology to RuBee.Most

Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin

Science.gov (United States)

Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo

2016-02-01

Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

Methanol oxidation catalysis and substructure of PtRu bimetallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Nitani, Hiroaki; Nakagawa, Takashi; Ono, Takahiro; Honda, Yusuke; Koizumi, Akiko; Seino, Satoshi; Yamamoto, Takao A. [Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan); Daimon, Hideo; Kurobe, Yukiko [Development and Technology Division, Hitachi Maxell Ltd., 6-20-1 Kinunodai, Tsukubamirai, Ibaraki 300-2496 (Japan)

2007-07-15

Catalytic material of PtRu nanoparticles supported on carbon (PtRu/C) for direct methanol fuel cells was synthesized by a polyol reduction method. Addition of phosphorus was effective for downsizing PtRu particles and improving their catalytic activity. The activity obtained was six times of that of a commercial catalysis. The samples were analyzed by techniques of X-ray absorption fine structure (XAFS) at Pt L{sub III}-edge and Ru K-edge, transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF). These results indicated a core-shell structure consisting of a Pt-rich core and Ru-rich shell. By examining coordination numbers determined by XAFS analysis, we found a clear correlation between the catalytic activity and the Pt-Ru atomic pair frequency occurring on the particle surface, which supports the 'bi-functional mechanism'. (author)

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.

Total Synthesis of Bryostatins. Development of Methodology for Atom-Economic and Stereoselective Synthesis of the C-ring Subunit

Science.gov (United States)

Trost, Barry M.; Frontier, Alison J.; Thiel, Oliver R.; Yang, Hanbiao; Dong, Guangbin