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Sample records for stable p-heterocyclic carbenes

  1. Cyclic (alkyl)(amino)carbenes (CAACs): stable carbenes on the rise.

    PubMed

    Soleilhavoup, Michèle; Bertrand, Guy

    2015-02-17

    CONSPECTUS: Carbenes are compounds that feature a divalent carbon atom with only six electrons in its valence shell. In the singlet state, they possess a lone pair of electrons and a vacant orbital and therefore exhibit Lewis acidic and Lewis basic properties, which explains their very high reactivity. Following the preparation by our group in 1988 of the first representative, a variety of stable carbenes are now available, the most popular being the cyclic diaminocarbenes. In this Account, we discuss another class of stable cyclic carbenes, namely, cyclic (alkyl)(amino)carbenes (CAACs), in which one of the electronegative and ?-donor amino substituents of diaminocarbenes is replaced by a ?-donating but not ?-donating alkyl group. As a consequence, CAACs are more nucleophilic (?-donating) but also more electrophilic (?-accepting) than diaminocarbenes. Additionally, the presence of a quaternary carbon in the position ? to the carbene center provides steric environments that differentiate CAACs dramatically from all other ligands. We show that the peculiar electronic and steric properties of CAACs allow for the stabilization of unusual diamagnetic and paramagnetic main group element species. As examples, we describe the preparation of room temperature stable phosphorus derivatives in which the heteroatom is in the zero oxidation state, nucleophilic boron compounds, and phosphorus-, antimony-, boron-, silicon-, and even carbon-centered neutral and cationic radicals. CAACs are also excellent ligands for transition metal complexes. The most recent application is their use for the stabilization of paramagnetic complexes, in which the metal is often in a formal zero oxidation state. Indeed, bis(CAAC)M complexes in which the metal is gold, copper, cobalt, iron, nickel, manganese, and zinc have been isolated. Depending on the metal, the majority of spin density can reside either on the metal or on the carbene carbons and the nitrogen atoms of the CAAC ligand. In contrast to diaminocarbenes, the higher basicity of CAACs makes them poor leaving groups, and thus they cannot be used for classical organocatalysis. However, because of their superior electrophilicity and smaller singlet-triplet gap, CAACs can activate small molecules at room temperature, such as CO, H2, and P4, as well as enthalpically strong bonds, such as B-H, Si-H, N-H, and P-H. Lastly, excellent results have been obtained in palladium, ruthenium, and gold catalysis. CAAC-metal complexes are extremely thermally robust, which allows for their utilization in harsh conditions. This property has been used to perform a variety of gold-catalyzed reactions in the presence of basic amines, including ammonia and hydrazine, which usually deactivate catalysts. PMID:25515548

  2. Stable Cyclic Carbenes and Related Species beyond Diaminocarbenes

    PubMed Central

    Melaimi, Mohand; Soleilhavoup, Michèle

    2011-01-01

    The success of homogeneous catalysis can be attributed largely to the development of a diverse range of ligand frameworks that have been used to tune the behavior of various systems. Spectacular results in this area have been achieved using cyclic diaminocarbenes (NHCs) as a result of their strong ?-donor properties. Although it is possible to cursorily tune the structure of NHCs, any diversity is still far from matching their phosphorus-based counterparts, which is one of the great strengths of the latter. A variety of stable acyclic carbenes are known, but they are either reluctant to bind metals or they give rise to fragile metal complexes. During the last five years, new types of stable cyclic carbenes, as well as related carbon-based ligands (which are not NHCs), and which feature even stronger ?-donor properties have been developed. Their synthesis and characterization as well as the stability, electronic properties, coordination behavior, and catalytic activity of the ensuing complexes are discussed, and comparisons with their NHC cousins are made. PMID:20836099

  3. Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold

    NASA Astrophysics Data System (ADS)

    Crudden, Cathleen M.; Horton, J. Hugh; Ebralidze, Iraklii I.; Zenkina, Olena V.; McLean, Alastair B.; Drevniok, Benedict; She, Zhe; Kraatz, Heinz-Bernhard; Mosey, Nicholas J.; Seki, Tomohiro; Keske, Eric C.; Leake, Joanna D.; Rousina-Webb, Alexander; Wu, Gang

    2014-05-01

    Since the first report of thiol-based self-assembled monolayers (SAMs) 30 years ago, these structures have been examined in a huge variety of applications. The oxidative and thermal instabilities of these systems are widely known, however, and are an impediment to their widespread commercial use. Here, we describe the generation of N-heterocyclic carbene (NHC)-based SAMs on gold that demonstrate considerably greater resistance to heat and chemical reagents than the thiol-based counterparts. This increased stability is related to the increased strength of the gold-carbon bond relative to that of a gold-sulfur bond, and to a different mode of bonding in the case of the carbene ligand. Once bound to gold, NHCs are not displaced by thiols or thioethers, and are stable to high temperatures, boiling water, organic solvents, pH extremes, electrochemical cycling above 0 V and 1% hydrogen peroxide. In particular, benzimidazole-derived carbenes provide films with the highest stabilities and evidence of short-range molecular ordering. Chemical derivatization can be employed to adjust the surface properties of NHC-based SAMs.

  4. A Stable Planar-Chiral N-Heterocyclic Carbene with a 1,1'-Ferrocenediyl Backbone.

    PubMed

    Petrov, Alex R; Derheim, Anatoli; Oetzel, Jan; Leibold, Michael; Bruhn, Clemens; Scheerer, Stefan; Oßwald, Steffen; Winter, Rainer F; Siemeling, Ulrich

    2015-07-01

    This paper focuses on the stable, ferrocene-based N-heterocyclic carbene (NHC) rac-[Fe{(?(5)-t-BuC5H3)NpN}2C:] (A'-Np, Np = neopentyl), which is planar-chiral due to the two tert-butyl substituents in 3,3'-positions. A'-Np was synthesized in nine steps starting from 1,1'-di-tert-butylferrocene (1), the first step being its 3,3'-dilithiation to afford rac-[Fe(?(5)-t-BuC5H3Li)2] (rac-fc'Li2, 2). The structures of rac-fc'(SiMe3)2 (3), rac-fc'Br2 (4), rac-fc'(N3)2 (5), and the immediate carbene precursor [A'-NpH]BF4 were determined by single-crystal X-ray diffraction (XRD). The chemical properties of A'-Np were found to be very similar to those of its tert-butyl-free congener A-Np, both being ambiphilic NHCs with rather high calculated HOMO energies (ca. -4.0 eV) and low singlet-triplet gaps (ca. 35 kcal/mol). A Tolman electronic parameter value of 2050 cm(-1) was derived from IR data of cis-[RhCl(A'-Np)(CO)2], indicating the high donicity of A'-Np as a ligand. Consistent with its ambiphilic nature, A'-Np was found to react readily with carbon monoxide, affording the betainic enolate (A'-Np)2CO as four stereoisomers, viz. (RpRp-A'-Np)?C(O(-))(RpRp-A'-Np(+)), (SpSp-A'-Np)?C(O(-))(SpSp-A'-Np(+)), (RpRp-A'-Np)?C(O(-))(SpSp-A'-Np(+)), and (SpSp-A'-Np)?C(O(-))(RpRp-A'-Np(+)). The former two isomers were structurally characterized as a racemic compound by single-crystal XRD. A'-Np was found to react swiftly with dichloromethane, affording the addition product A'-NpH-CHCl2 in a reaction that is unprecedented for diaminocarbenes. A-NpH-CHCl2 was obtained analogously. Both compounds were structurally characterized by single-crystal XRD. An electrochemical investigation of A'-Np by cyclic and square wave voltammetry revealed a reversible oxidation of the carbene at a half-wave potential of -0.310 vs ferrocene/ferrocenium (THF/NBu4PF6). The electrochemical data previously published for A-Np were identified to be incorrect, since unnoticed hydrolysis of the NHC had taken place, affording A-Np(H2O). The hydrolysis products of A-Np and A'-Np were found to be reversibly oxidized at half-wave potentials of -0.418 and -0.437 V, respectively. PMID:26098133

  5. Stable N-heterocyclic carbene adducts of arylchlorosilylenes and their germanium homologues.

    PubMed

    Filippou, Alexander C; Chernov, Oleg; Blom, Burgert; Stumpf, Kai W; Schnakenburg, Gregor

    2010-03-01

    The first N-heterocyclic carbene adducts of arylchlorosilylenes are reported and compared with the homologous germanium compounds. The arylsilicon(II) chlorides SiArCl(Im-Me(4)) [Ar=C(6)H(3)-2,6-Mes(2) (Mes=C(6)H(2)-2,4,6-Me(3)), C(6)H(3)-2,6-Trip(2) (Trip=C(6)H(2)-2,4,6-iPr(3))] were obtained selectively on dehydrochlorination of the arylchlorosilanes SiArHCl(2) with 1,3,4,5-tetramethylimidazol-2-ylidene (Im-Me(4)). The analogous arylgermanium(II) chlorides GeArCl(Im-Me(4)) were prepared by metathetical exchange of GeCl(2)(Im-Me(4)) with LiC(6)H(3)-2,6-Mes(2) or addition of Im-Me(4) to GeCl(C(6)H(3)-2,6-Trip(2)). All compounds were fully characterized. Density functional calculations on ECl(C(6)H(3)-2,6-Trip(2))(Im-Me(4)), where E=Si, Ge, at different levels of theory show very good agreement between calculated and experimental bonding parameters, and NBO analyses reveal similar electronic structures of the two aryltetrel(II) chlorides. The low gas-phase Gibbs free energy of bond dissociation of SiCl(C(6)H(3)-2,6-Trip(2))(Im-Me(4)) (Delta(calcd) degrees=28.1 kJ mol(-1)) suggests that the carbene adducts SiArCl(Im-Me(4)) may be valuable transfer reagents of the arylsilicon(II) chlorides SiArCl. PMID:20077546

  6. Carbene Catalysts

    NASA Astrophysics Data System (ADS)

    Moore, Jennifer L.; Rovis, Tomislav

    The use of N-heterocyclic carbenes as catalysts for organic transformations has received increased attention in the past 10 years. A discussion of catalyst development and nucleophilic characteristics precedes a description of recent advancements and new reactions using N-heterocyclic carbenes in catalysis.

  7. A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf-Stable Carbene Borane Complexes

    PubMed Central

    Hoshimoto, Yoichi; Kinoshita, Takuya; Ohashi, Masato; Ogoshi, Sensuke

    2015-01-01

    N-Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6F5)3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm–B(C6F5)3 complexes so that reactivation only occurred above ambient temperature. PMID:26315680

  8. Carbenes and Nitrenes

    ERIC Educational Resources Information Center

    Coyle, J. D.

    1974-01-01

    Summarizes the general methods for carbene and nitrene formation and the reactions in which carbenes and nitrenes are involved such as their reactions with transition metal atoms, alkenes of aromatic compounds, and uncharged oxygen or nitrogen nucleophiles. (CC)

  9. Carbene-dichlorosilylene stabilized phosphinidenes exhibiting strong intramolecular charge transfer transition.

    PubMed

    Roy, Sudipta; Stollberg, Peter; Herbst-Irmer, Regine; Stalke, Dietmar; Andrada, Diego M; Frenking, Gernot; Roesky, Herbert W

    2015-01-14

    The unstable species dichlorosilylene was previously stabilized by carbene. The lone pair of electrons on the silicon atom of (carbene)SiCl2 can form a coordinate bond with metal-carbonyls. Herein we report that (carbene)SiCl2 can stabilize a phosphinidene (Ar-P, a carbone analogue) with the general formula carbene?SiCl2?P-Ar (carbene = cyclic alkyl(amino) carbene (cAAC; 2) and N-heterocyclic carbene (NHC; 3)). Compounds 2 and 3 are stable, isolable, and storable at 0 °C (2) to room temperature (3) under an inert atmosphere. The crystals of 2 and 3 are dark blue and red, respectively. The intense blue color of 2 arises due to the strong intramolecular charge transfer (ICT) transition from ?Si?P??*cAAC. The electronic structure and bonding of 2, 3 were studied by theoretical calculations. The HOMO of the molecule is located on the ?Si?P bond, while the LUMO is located at the carbene moiety (cAAC or NHC). The dramatic change in color of these compounds from red (3, NHC) to blue (2, cAAC) is ascribed to the difference in energy of the LUMO within the carbenes (cAAC/NHC) due to a lower lying LUMO of cAAC. PMID:25539016

  10. Are copper(I) carbenes capable intermediates for cyclopropanations? The case for ylide intermediates.

    PubMed

    Aldajaei, Jamal T; Keeffe, James R; Swift, Christopher A; Gronert, Scott

    2015-09-01

    A novel approach is used to synthesize a stable, ligated copper(I) carbene in the gas phase that is capable of typical metal carbenoid chemistry. However, it is shown that copper(I) carbenes generally undergo rapid unimolecular rearrangements including insertions into copper-ligand bonds and Wolff rearrangements. The results indicate that most copper(I) carbenes are inherently unstable and would not be viable intermediates in condensed-phase applications; an alternative intermediate that is less prone to rearrangements is required. Computational data suggest that ylides formed by the complexation of the carbene with solvent or other weak nucleophiles are viable intermediates in the reactions of copper(I) carbenes. PMID:26179611

  11. A persistent (amino)(ferrocenyl)carbene†‡

    PubMed Central

    DeHope, Alan; Mendoza-Espinosa, Daniel; Donnadieu, Bruno

    2012-01-01

    Deprotonation of N,N-diisopropyl-C-ferrocenylaldiminium triflate 2 cleanly leads to the corresponding 1,2-diamino-1,2-diferrocenylethene 3, the dimer of the desired (amino)(ferrocenyl)carbene. Fulvene 6, obtained by addition of the lithium salt of tetramethylcyclopentadiene to methoxyformamidinium methylsulfate 5, reacts with dicarbonylcyclopentadienylbromoiron(II), and with a mixture of FeCl2 and Cp* lithium salt, affording the corresponding tetramethylferrocenylaldiminium salt 7, and nonamethylferrocenylaldiminium salt 8, respectively. Although the deprotonation of 7 gives a complex mixture of products, the treatment of 8 at ?78 °C with sodium hexamethyldisilazide allowed for the isolation of the corresponding (amino)(ferrocenyl)carbene 9 as a yellow powder. However, even in the solid state, it is stable for less than 48 h at ?20 °C. In addition to NMR spectroscopy, evidence for the carbene nature of 9 was found by a trapping experiment with sulfur that leads to the corresponding adduct 10, which was characterized by a single crystal X-ray diffraction study. PMID:22707878

  12. Different electronic structure of phosphonyl radical adducts of N-heterocyclic carbenes, silylenes and germylenes: EPR spectroscopic study and DFT

    E-print Network

    Apeloig, Yitzhak

    Different electronic structure of phosphonyl radical adducts of N-heterocyclic carbenes, silylenes 18th March 2010 DOI: 10.1039/c0sc00143k Stable N-heterocyclic carbenes and germylenes were allowed of the radical adducts of the different (C, Si, Ge) unsaturated N-heterocyclic divalent species

  13. Synthesis and Properties of Chelating N-Heterocyclic Carbene Rhodium(I) Complexes: Synthetic Experiments in Current Organometallic Chemistry

    ERIC Educational Resources Information Center

    Mata, Jose A.; Poyatos, Macarena; Mas-Marza, Elena

    2011-01-01

    The preparation and characterization of two air-stable Rh(I) complexes bearing a chelating N-heterocyclic carbene (NHC) ligand is described. The synthesis involves the preparation of a Ag(I)-NHC complex and its use as carbene transfer agent to a Rh(I) precursor. The so obtained complex can be further reacted with carbon monoxide to give the…

  14. Steroid Derived Mesoionic Gold and Silver Mono- and Polymetallic Carbenes.

    PubMed

    Frutos, María; de la Torre, María C; Sierra, Miguel A

    2015-12-01

    A two-step synthesis of gold mesoionic carbene complexes containing estrone moieties has been developed. The method uses the methylation of the triazole nucleus, followed by the treatment of the triazolium salt with Ag2O and transmetalation with [AuCl(SMe2)]. Mono-, bi-, tri-, and tetrametallic gold complexes can be obtained depending on the structure of the starting triazolium salts. Tetrametallic gold carbene embedded in a macrocylic stereoidal cavity containing four estrone nuclei has been also prepared. Additionally, the mono- and bimetallic silver carbene complexes containing triazole-steroid ligands have been isolated and characterized. These complexes resulted to be stable and have been characterized by spectroscopic and HRMS techniques. The gold and silver complexes having triazole-steroid ligands are unprecedented in the literature and the method reported here to access to these compounds is easy and efficient. Preliminary results regarding the catalytic activity of some of the gold-carbenes prepared in the insertion of diazoalkanes into alcohols are presented. PMID:26600185

  15. Gold Carbene or Carbenoid: Is There a Difference?

    PubMed Central

    Wang, Yahui; Muratore, Michael E; Echavarren, Antonio M

    2015-01-01

    By reviewing the recent progress on the elucidation of the structure of gold carbenes and the definitions of metal carbenes and carbenoids, we recommend to use the term gold carbene to describe gold carbene-like intermediates, regardless of whether the carbene or carbocation extreme resonance dominates. Gold carbenes, because of the weak metal-to-carbene ?-back-donation and their strongly electrophilic reactivity, could be classified into the broader family of Fischer carbenes, although their behavior and properties are very specific. PMID:25786384

  16. Computational Chemistry Studies on the Carbene Hydroxymethylene

    ERIC Educational Resources Information Center

    Marzzacco, Charles J.; Baum, J. Clayton

    2011-01-01

    A density functional theory computational chemistry exercise on the structure and vibrational spectrum of the carbene hydroxymethylene is presented. The potential energy curve for the decomposition reaction of the carbene to formaldehyde and the geometry of the transition state are explored. The results are in good agreement with recent…

  17. Exotic noble gas carbene-like ions

    NASA Astrophysics Data System (ADS)

    Echeverri, Andrea; Moreno, Norberto; Restrepo, Albeiro; Hadad, C. Z.

    2014-11-01

    Using a combination of theoretical techniques, this work studies the Kr2C2+ species, which has electronic, structural, and some typical chemical characteristics of carbenes, and whose ground state is singlet. Similarly to the case of traditional carbenes, Kr2C2+ is metastable and appears to be a candidate for a reactive intermediate.

  18. A Three-Step Laboratory Sequence to Prepare a Carbene Complex of Silver(I) Chloride

    ERIC Educational Resources Information Center

    Canal, John P.; Ramnial, Taramatee; Langlois, Lisa D.; Abernethy, Colin D.; Clyburne, Jason A. C.

    2008-01-01

    We have developed a multistep inorganic synthesis experiment for our second-year undergraduate teaching laboratory that introduces students to modern organometallic chemistry. The ligands are prepared in two simple steps and the preparation of an air-stable silver carbene complex is accomplished in the third step. The students are introduced to…

  19. N-Heterocyclic Carbene-Catalyzed Alcohol Acetylation: An Organic Experiment Using Organocatalysis

    ERIC Educational Resources Information Center

    Morgan, John P.; Shrimp, Jonathan H.

    2014-01-01

    Undergraduate students in the teaching laboratory have successfully used N-heterocyclic carbenes (NHCs) as organocatalysts for the acetylation of primary alcohols, despite the high water sensitivity of uncomplexed ("free") NHCs. The free NHC readily reacted with chloroform, resulting in an air- and moisture-stable adduct that liberates…

  20. A DFT and structural investigation of the conformations of Fischer carbene complexes

    NASA Astrophysics Data System (ADS)

    Landman, Marilé

    2015-09-01

    A set of different Fischer carbene complexes of group VI and VII metals, with varied heteroatom and heteroaromatic substituents on the carbene carbon atom, was studied. Density functional theory as well as single crystal diffraction techniques were employed to investigated the most stable conformation of these complexes. The complexes studied, [M(CO)4L{C(X)Z}], with L = PPh3 or CO, X = ethoxy (-OCH2CH3) or amino (-NH2 or NHCy) substituents as the heteroatom carbene substituents, Z = 2-furyl (-C4H3O), 2-thienyl (-C4H3S), 2-(N-methyl)pyrrolyl (-C4H3NCH3) as the second carbene substituent had their substituents varied systematically to give all the possible conformations of these complexes. The conformations of the complexes, in particular the relative orientations of the heteroatoms in the molecule (syn vs. anti), E/Z isomerism in the aminocarbene complexes and cis/trans isomerism in the ligand substituted complexes as well as various combinations of these aspects, were studied. In general, it was found that the most stable conformation theoretically as well as in the solid state for most of the complexes preferred the syn conformation. The Z-isomer is generally preferred over the E isomer while the cis is more predominant than the trans isomer. Using DFT and NBO calculations, explanations for the preferred conformations were explored. It was concluded that both steric and electronic factors influence the conformations of the carbene complexes, with the extent of contribution of these two factors varying for each of the different carbene substituents.

  1. Crystalline Cyclic (Alkyl)(amino)carbene-tetrafluoropyridyl Radical.

    PubMed

    Styra, Steffen; Melaimi, Mohand; Moore, Curtis E; Rheingold, Arnold L; Augenstein, Timo; Breher, Frank; Bertrand, Guy

    2015-06-01

    A stable cyclic (alkyl)(amino)carbene (CAAC) 1 inserts into the para-CF bond of pentafluoropyridine, and after fluoride abstraction, the iminium-pyridyl adduct [3](+) was isolated. A cyclic voltammetry study shows a reversible three-state redox system involving [3](+) , [3](?) , and [3](-) . The CAAC-pyridyl radical [3](?) , obtained by reduction of [3](+) with magnesium, has been spectroscopically and crystallographically characterized. In contrast to the lack of ? communication between the CAAC and the pyridine units in cation [3](+) , the unpaired electron of [3](?) is delocalized over an extended ? system involving both heterocycles. PMID:25925367

  2. Electropositive metal N-heterocyclic carbene complexes 

    E-print Network

    Casely, Ian J.

    2009-01-01

    The first chapter is an introduction to the f-elements, with a focus on the synthesis and chemistry of tetravalent cerium complexes. The synthesis, characterisation and reactivity of carbenes, particularly N-heterocyclic ...

  3. Carbene formation upon reactive dissolution of metal oxides in imidazolium ionic liquids.

    PubMed

    Wellens, Sil; Brooks, Neil R; Thijs, Ben; Meervelt, Luc Van; Binnemans, Koen

    2014-03-01

    Metal oxides were found to dissolve in different imidazolium ionic liquids with a hydrogen atom in the C2 position of the imidazolium ring, but not if a methyl substituent was present in the C2 position. The crystal structure of the product that crystallised from an ionic liquid containing dissolved silver(i) oxide showed that this was a silver(i) carbene complex. The presence of carbenes in solution was proven by (13)C NMR spectroscopy and the reactions were also monitored by Raman spectroscopy. The dissolution of other metal oxides, namely copper(ii) oxide, zinc(ii) oxide and nickel(ii) oxide, was also studied in imidazolium ionic liquids and it was found that stable zinc(ii) carbenes were formed in solution, but these did not crystallise under the given experimental conditions. A crystalline nickel(ii) carbene complex could be obtained from a solution of nickel(ii) chloride dissolved in a mixture of 1-butyl-3-methylimidazolium and 1-ethyl-3-methylimidazolium acetate. PMID:24390601

  4. Frustrated N-heterocyclic carbene-silylium ion Lewis pairs.

    PubMed

    Silva Valverde, Miguel F; Theuergarten, Eileen; Bannenberg, Thomas; Freytag, Matthias; Jones, Peter G; Tamm, Matthias

    2015-05-28

    The reaction of the N-heterocyclic carbene 1,3-di-tert-butyl-4,5-dimethylimidazolin-2-ylidene () with trimethylsilyl iodide, triflate and triflimidate [Me3SiX, X = I, CF3SO3 (OTf), (CF3SO2)2N (NTf2)] by mixing the neat, liquid starting materials afforded the corresponding 2-(trimethylsilyl)imidazolium salts [()SiMe3]X as highly reactive, white crystalline solids. Only the triflimidate (X = NTf2) proved to be stable in solution and could be characterized by means of NMR spectroscopy (in C6D5Br) and X-ray diffraction analysis, whereas dissociation into free and Me3SiOTf was observed for the triflate system, in agreement with the trend derived by DFT calculations; the iodide was too insoluble for characterization. The compounds [()SiMe3]X showed the reactivity expected for frustrated carbene-silylium pairs, and treatment with carbon dioxide, tert-butyl isocyanate and diphenylbutadiyne gave the 1,2-addition products [()CO2SiMe3]X (X = I, OTf, NTf2), [()C(NtBu)OSiMe3]OTf and [()C(Ph)C(SiMe3)CCPh]OTf, respectively. Upon reaction with [AuCl(PPh3)], metal-chloride bond activation was observed, with formation of the cationic gold(i) complexes [()Au(PPh3)]X (X = OTf, NTf2). PMID:25912291

  5. Ru-Based Z-Selective Metathesis Catalysts with Modified Cyclometalated Carbene Ligands†

    PubMed Central

    Bronner, Sarah M.; Herbert, Myles B.; Patel, Paresma R.; Marx, Vanessa M.; Grubbs, Robert H.

    2014-01-01

    A series of cyclometalated Z-selective ruthenium olefin metathesis catalysts with alterations to the N-heterocyclic carbene (NHC) ligand were prepared. X-Ray crystal structures of several new catalysts were obtained, elucidating the structural features of this class of cyclometalated complexes. The metathesis activity of each stable complex was evaluated, and one catalyst, bearing geminal dimethyl backbone substitution, was found to be comparable to our best Z-selective metathesis catalyst to date. PMID:25346842

  6. First Chelated Chiral N-Heterocyclic Bis-Carbene Complexes

    E-print Network

    RajanBabu, T. V. "Babu"

    First Chelated Chiral N-Heterocyclic Bis-Carbene Complexes Dean S. Clyne, Jian Jin, Evan Genest metal complexes of N-heterocyclic car- benes,1 received little attention until the report of free metal under catalytic condi- tions.3,4 The N-heterocyclic carbene complexes have been applied

  7. FOCUS REVIEW N-Heterocyclic carbene-catalyzed dimerization,

    E-print Network

    Cai, Long

    FOCUS REVIEW N-Heterocyclic carbene-catalyzed dimerization, cyclotetramerization and polymerization of Michael acceptors Shin-ichi Matsuoka N-Heterocyclic carbenes (NHCs), which were first isolated, however, Arduengo et al. made a major breakthrough in isolating the first crystalline nucleophilic N-heterocyclic

  8. Protonation of Homoenolate Equivalents Generated by N-Heterocyclic Carbenes

    PubMed Central

    Maki, Brooks E.; Chan, Audrey; Scheidt, Karl A.

    2010-01-01

    Homoenolate equivalents are generated by Lewis basic N-heterocyclic carbene catalysts and then protonated to generate efficiently saturated esters from unsaturated aldehydes. This reactivity is extended to the generation of ?-acylvinyl anions from alkynyl aldehydes. The asymmetric protonation of a homoenolate equivalent generated from a ?,?-disubstituted aldehyde can be accomplished with a chiral N-heterocyclic carbene. PMID:22347730

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

    PubMed

    Schmid, Thibault E; Modicom, Florian; Dumas, Adrien; Borré, Etienne; Toupet, Loic; Baslé, Olivier; Mauduit, Marc

    2015-01-01

    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)(picolinate)RuCl(indenylidene) complex 4a (SIPr = 1,3-bis(2-6-diisopropylphenyl)imidazolidin-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. PMID:26425213

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

    PubMed Central

    Schmid, Thibault E; Modicom, Florian; Dumas, Adrien; Borré, Etienne; Toupet, Loic

    2015-01-01

    Summary 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)(picolinate)RuCl(indenylidene) complex 4a (SIPr = 1,3-bis(2-6-diisopropylphenyl)imidazolidin-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. PMID:26425213

  11. Diverse Chemical Applications of N-Heterocyclic Carbenes N-Heterocyclic carbenes, or NHCs as they are commonly abbreviated, have attracted

    E-print Network

    Jones, William D.

    Diverse Chemical Applications of N-Heterocyclic Carbenes N-Heterocyclic carbenes, or NHCs that include an assortment of heterocyclic substituents. Another use of an NHC in organocatalysis was reported polymerization to give R,- difunctionalized PEOs with polydipersities near 1.0.4 N-Heterocyclic carbenes have

  12. Poly(fluoroalkyl acrylate)-bound ruthenium carbene complex: a fluorous and recyclable catalyst for ring-closing olefin metathesis.

    PubMed

    Yao, Qingwei; Zhang, Yiliang

    2004-01-14

    The synthesis of a fluorous olefin metathesis catalyst derived from the Grubbs second-generation ruthenium carbene complex is described. The air stable fluorous polymer-bound ruthenium carbene complex 1 shows high reactivity in effecting the ring-closing metathesis of a broad spectrum of diene and enyne substrates leading to the formation of di-, tri-, and tetrasubstituted cyclic olefins in minimally fluorous solvent systems (PhCF3/CH2Cl2, 1:9-1:49 v/v). The catalyst can be readily separated from the reaction mixture by fluorous extraction with FC-72 and repeatedly reused. The practical advantage offered by the fluorous catalyst is demonstrated by its sequential use in up to five different metathesis reactions. PMID:14709066

  13. Annulated boron substituted N-heterocyclic carbenes: theoretical prediction of highly electrophilic carbenes.

    PubMed

    Bharadwaz, Priyam; Borthakur, Bitupon; Phukan, Ashwini K

    2015-11-14

    Theoretical calculations were carried out to understand the effect of annulation on the electronic and ligand properties of boron substituted N-heterocyclic carbenes (B-NHCs). Annulation results in a decrease in stability as indicated by the calculated values of singlet-triplet separations and stabilization energies as well as HOMO-LUMO gaps. Annulated B-NHCs are found to be weaker ?-donors but better ?-acceptors than the parent ones. The decrease in ?-donation ability and the increase in ?-accepting ability are further supported by the calculated values of proton affinities, nucleophilicity and electrophilicity indices as well as (31)P NMR chemical shifts of the corresponding NHC-PPh adducts. Most of the annulated B-NHCs are found to have significantly enhanced electrophilicity than the other known carbenes. PMID:26455836

  14. Palladium-Catalyzed Intermolecular Carbene Insertion Prior to Intramolecular Heck Cyclization: Synthesis of 2-Arylidene-3-aryl-1-indanones.

    PubMed

    Arunprasath, Dhanarajan; Muthupandi, Pandi; Sekar, Govindasamy

    2015-11-01

    A domino process that converges the migratory insertion of carbene with a Heck reaction has been established as a versatile tool for the synthesis of 2-arylidene-3-aryl-1-indanones from very stable and easily accessible N-tosylhydrazones and 2'-iodochalcones. The reaction selectively proceeds through 5-exo-trig cyclization and delivers the products selectively with the E configuration of the double bond in excellent yields. The one-pot synthesis of 2-arylidene-3-aryl-1-indanones involving in situ synthesis of both 2'-iodochalcones and N-tosylhydrazones has also been demonstrated. PMID:26501560

  15. Bis-N-heterocyclic Carbene Aminopincer Ligands Enable High Activity in Ru-Catalyzed Ester Hydrogenation.

    PubMed

    Filonenko, Georgy A; Aguila, Mae Joanne B; Schulpen, Erik N; van Putten, Robbert; Wiecko, Jelena; Müller, Christian; Lefort, Laurent; Hensen, Emiel J M; Pidko, Evgeny A

    2015-06-24

    Bis-N-heterocyclic carbene (NHC) aminopincer ligands were successfully applied for the first time in the catalytic hydrogenation of esters. We have isolated and characterized a well-defined catalyst precursor as a dimeric [Ru2(L)2Cl3]PF6 complex and studied its reactivity and catalytic performance. Remarkable initial activities up to 283,000 h(-1) were achieved in the hydrogenation of ethyl hexanoate at only 12.5 ppm Ru loading. A wide range of aliphatic and aromatic esters can be converted with this catalyst to corresponding alcohols in near quantitative yields. The described synthetic protocol makes use of air-stable reagents available in multigram quantities, rendering the bis-NHC ligands an attractive alternative to the conventional phosphine-based systems. PMID:26052835

  16. Superior Oxygen Stability of N-Heterocyclic Carbene-Coated Au Nanocrystals: Comparison with Dodecanethiol.

    PubMed

    Ling, Xiang; Schaeffer, Nicolas; Roland, Sylvain; Pileni, Marie-Paule

    2015-12-01

    The stability of Au nanocrystals (NCs) coated with different N-heterocyclic carbenes (NHCs) or dodecanethiol (DDT) to oxygen-based treatments was investigated. A dominant effect of the ligand type was observed with a significantly greater oxygen resistance of NHC-coated Au NCs compared to that of the thiol-based analogues. NHC-coated Au NCs are stable to 10 W oxygen plasma etching for up to 180 s whereas the integrity of DDT-coated Au NCs is strongly affected by the same treatment from 60-80 s. In the latter case, the average size of the NCs (from 2.6 to 6.3 nm) and the method of synthesis have no effect on the stability. NHC-coated Au NCs were found to generate of a smaller quantity of ligand-derived species under molecular oxygen treatment, which could account for the increased stability. PMID:26550843

  17. Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

    SciTech Connect

    Gottlieb, C.A.; Thaddeus, P.

    1993-12-01

    Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

  18. Fischer and Schrock Carbene Complexes: A Molecular Modeling Exercise

    ERIC Educational Resources Information Center

    Montgomery, Craig D.

    2015-01-01

    An exercise in molecular modeling that demonstrates the distinctive features of Fischer and Schrock carbene complexes is presented. Semi-empirical calculations (PM3) demonstrate the singlet ground electronic state, restricted rotation about the C-Y bond, the positive charge on the carbon atom, and hence, the electrophilic nature of the Fischer…

  19. Copper and Silver Carbene Complexes without Heteroatom-Stabilization: Structure, Spectroscopy, and Relativistic Effects.

    PubMed

    Hussong, Matthias W; Hoffmeister, Wilhelm T; Rominger, Frank; Straub, Bernd F

    2015-08-24

    Salts of a copper and a silver carbene complex were prepared from dimesityl diazomethane, made possible by the steric shielding of the N-heterocyclic carbene (NHC) ancillary ligand IPr**. The mint-green complex [IPr**Ag=CMes2 ](+) [NTf2 ](-) is the first isolated silver carbene complex without heteroatom donor substituents. Single-crystal X-ray diffraction provides evidence for a predominant carbenoid character, and supports the postulation of such reactive species as intermediates in silver-catalyzed C-H activation reactions. The greenish yellow copper carbene complex [IPr**Cu=CMes2 ](+) [NTf2 ](-) has spectroscopic properties in between the isostructural silver complex and the already reported emerald green gold carbene complex. A comparison in the Group?11 series indicates that relativistic effects are responsible for the strong ??bond and the significant ??back-bonding in the gold carbene moiety. PMID:26189567

  20. Cooperative Lewis acid/N-heterocyclic carbene catalysis

    PubMed Central

    Cohen, Daniel T.; Scheidt, Karl A.

    2015-01-01

    Lewis acid activation with N-heterocyclic carbene (NHC) catalysis has presented new opportunities for enantioselective reaction development. Recent findings illustrate that Lewis acids can play an important role in homoenolate annulations by: enhancement of the reactivity, reversal of the diastereo- or regioselectivity, and activation of previously inactive electrophiles. Additionally, the incorporation of a Lewis acid into Brønsted base-catalyzed conjugate addition allowed for an increase in yields. PMID:26413259

  1. Thesis proposal CSF Brazil 2014 Planar chiral N-heterocyclic carbene ferrocenyl ligands for asymmetric catalysis

    E-print Network

    Bordenave, Charles

    Thesis proposal CSF Brazil 2014 Title: Planar chiral N-heterocyclic carbene ferrocenyl ligands of the reaction. Our group has a strong know-how in the design of functionalized (chiral) N-heterocyclic carbene of indanes.[5] Our group has a strong know-how in the design of functionalized (chiral) N-heterocyclic

  2. Tripletsinglet energy gaps in iodo-carbenes (ICX): Remarkable discrepancy between theory and experiment

    E-print Network

    Nguyen, Minh Tho

    Triplet­singlet energy gaps in iodo-carbenes (I­C­X): Remarkable discrepancy between theory published as an Advance Article on the web 30th October 2000 The tripletÈsinglet energy gaps in iodo study conÐrms the singlet character of other iodo-carbenes with substantial tripletÈsinglet gaps

  3. The Depolymerization of Poly(Ethylene Terephthalate) (PET) Using N-Heterocyclic Carbenes from Ionic Liquids

    ERIC Educational Resources Information Center

    Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate; Waymouth, Robert M.; Pratt, Russell C.; Nyce, Gregory W.; Hedrick, James L.

    2010-01-01

    The depolymerization of the plastic polyethylene terephthalate (PET or PETE) is described in this laboratory procedure. The transesterification reaction used to depolymerize PET employs a highly efficient N-heterocyclic carbene catalyst derived from a commercially available imidazolium ionic liquid. N-heterocyclic carbenes are potent nucleophilic…

  4. Si-H activation by means of metal ligand cooperation in a methandiide derived carbene complex.

    PubMed

    Weismann, Julia; Gessner, Viktoria H

    2015-09-24

    Si-H bond activation of a number of silanes via metal ligand cooperation in a carbene complex is reported. Thereby, the electronic flexibility of the carbene ligand allows for the activation via a unique mechanism with oxidative addition to an 18e species without a formal change in the number of valence electrons. PMID:26304998

  5. Organometallic rhenium(III) chalcogenide clusters: coordination of N-heterocyclic carbenes.

    PubMed

    Durham, Jessica L; Wilson, Wade B; Huh, Daniel N; McDonald, Robert; Szczepura, Lisa F

    2015-07-01

    The preparation of rhenium based octahedral clusters containing N-heterocyclic carbenes is described. These represent the first examples of [M6(?3-Q)8](n+) or [M6(?3-X)8](n+) clusters to contain a carbene ligand of any type (NHC, Fischer or Schrock). Surprisingly, the NHC ligands attenuate their luminescent properties. PMID:26041404

  6. Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex**

    PubMed Central

    Lu, Erli; Cooper, Oliver J; McMaster, Jonathan; Tuna, Floriana; McInnes, Eric J L; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2014-01-01

    We report the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)2] (5, BIPMTMS=C(PPh2NSiMe3)2; Mes=2,4,6-Me3C6H2; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPMTMS)(O)2(DMAP)2] (6). PMID:24842784

  7. Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex.

    PubMed

    Lu, Erli; Cooper, Oliver J; McMaster, Jonathan; Tuna, Floriana; McInnes, Eric J L; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2014-06-23

    We report the uranium(VI) carbene imido oxo complex [U(BIPM(TMS))(NMes)(O)(DMAP)2] (5, BIPM(TMS) = C(PPh2 NSiMe3)2; Mes = 2,4,6-Me3C6H2; DMAP = 4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM(TMS))(O)2(DMAP)2] (6). PMID:24842784

  8. Ruthenium-based complexes containing a benzimidazolium tag covalently connected to N-heterocyclic carbene ligands: environmentally friendly catalysts for olefin metathesis transformations.

    PubMed

    Klu?iar, Marek; Grela, Karol; Mauduit, Marc

    2013-05-28

    Two ruthenium-based pre-catalysts containing an ionic tag covalently connected to a N-heterocyclic carbene (NHC) ligand are reported. These novel complexes, bearing a polar benzimidazolium group, are air-stable and can be easily prepared from commercially available reagents. The quaternary benzimidazolium tag allows the efficient separation of ruthenium waste from the metathesis product after reaction. Application in several olefin metathesis transformations leads to desired products of high purity, which exhibit ruthenium contamination levels as low as 1 ppm after simple filtration through a pad of silica gel. PMID:23360984

  9. N-Heterocyclic carbene stabilized Ag-P nanoclusters.

    PubMed

    Khalili Najafabadi, Bahareh; Corrigan, John F

    2015-01-14

    The N-heterocyclic carbene (NHC) 1,3-di-isopropylbenzimidazole-2-ylidene ((i)Pr2-bimy) is found to be an excellent ligand for the stabilization of silver-phosphorus polynuclear complexes. The straightforward preparation and characterization of the clusters [Ag12(PSiMe3)6((i)Pr2-bimy)6] (1) and [Ag26P2(PSiMe3)10((i)Pr2-bimy)8] (2) are described, representing the first examples of such structurally characterized, higher nuclearity complexes obtained using this class of ligands. PMID:25415342

  10. The synthesis and structure of a carbene-stabilized iminocarboranyl-boron(i) compound.

    PubMed

    Wang, Hao; Zhang, Jiji; Lin, Zhenyang; Xie, Zuowei

    2015-12-01

    A carbene-stabilized iminocarboranylboron(i) compound has been synthesized and structurally characterized. Single-crystal X-ray analyses and DFT calculations show that the ? back donation of the lone pair of electrons on the boron(i) center onto the ?* orbital of the imine unit is crucial for removing the electron density of the boron center thereby stabilizing such species, in which the carbene serves solely as a ? donor. This work also demonstrates that imines play a similar role to that of carbenes in the stabilization of low valent boron compounds. PMID:26434636

  11. An abnormal N-heterocyclic carbene-carbon dioxide adduct from imidazolium acetate ionic liquids: the importance of basicity.

    PubMed

    Kelemen, Zsolt; Péter-Szabó, Barbara; Székely, Edit; Hollóczki, Oldamur; Firaha, Dzmitry S; Kirchner, Barbara; Nagy, József; Nyulászi, László

    2014-09-26

    In the reaction of 1-ethyl-3-methylimidazolium acetate [C2C1Im][OAc] ionic liquid with carbon dioxide at 125?°C and 10?MPa, not only the known N-heterocyclic carbene (NHC)-CO2 adduct I, but also isomeric aNHC-CO2 adducts II and III were obtained. The abnormal NHC-CO2 adducts are stabilized by the presence of the polarizing basic acetate anion, according to static DFT calculations and ab initio molecular dynamics studies. A further possible reaction pathway is facilitated by the high basicity of the system, deprotonating the initially formed NHC-CO2 adduct I, which can then be converted in the presence of the excess of CO2 to the more stable 2-deprotonated anionic abnormal NHC-CO2 adduct via the anionic imidazolium-2,4-dicarboxylate according to DFT calculations on model compounds. This suggests a generalizable pathway to abnormal NHC complex formation. PMID:25137312

  12. Carbene supported dimer of heavier ketenimine analogue with p and si atoms.

    PubMed

    Roy, Sudipta; Dittrich, Birger; Mondal, Totan; Koley, Debasis; Stückl, A Claudia; Schwederski, Brigitte; Kaim, Wolfgang; John, Michael; Vasa, Suresh Kumar; Linser, Rasmus; Roesky, Herbert W

    2015-05-20

    A cyclic alkyl(amino) carbene (cAAC) stabilized dimer [(cAAC)Si(P-Tip)]2 (2) (Tip = 2,4,6-triisopropylphenyl) is reported. 2 can be considered as a dimer of the heavier ketenimine (R2C?C?N-R) analogue. The dark-red rod-shaped crystals of 2 were synthesized by reduction of the precursor, cAAC-dichlorosilylene-stabilized phosphinidene (cAAC)SiCl2?P-Tip with sodium napthalenide. The crystals of 2 are storable at room temperature for several months and stable up to 215 °C under an inert atmosphere. X-ray single-crystal diffraction revealed that 2 contains a cyclic nonplanar four-membered SiPSiP ring. Magnetic susceptibility measurements confirmed the singlet spin ground state of 2. Cyclic voltammetry of 2 showed a quasi-reversible one-electron reduction indicating the formation of the corresponding radical anion 2(•-), which was further characterized by EPR measurements in solution. The electronic structure and bonding of 2 and 2(•-) were studied by theoretical calculations. The experimentally obtained data are in good agreement with the calculated values. PMID:25919008

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

    PubMed

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

    2015-05-20

    The synthesis, structure, and olefin metathesis activity of the first neutral and cationic W-oxo-alkylidene-N-heterocyclic carbene (NHC) catalysts are reported. Neutral W-oxo-alkylidene-NHC catalysts can be prepared in up to 90% isolated yield. Depending on the ligands used, they possess either an octahedral (Oh) or trigonal bipyramidal ligand sphere. They can be activated with excess AlCl3 to form cationic olefin metathesis-active W-complexes; however, these readily convert into neutral chloro-complexes. Well-defined, stable cationic species can be prepared by stoichiometric substitution of one chloro ligand in the parent, neutral W-oxo-alkylidene-NHC complexes with Ag(MeCN)2B(Ar(F))4 or NaB(Ar(F))4; B(Ar(F))4 = B(3,5-(CF3)2-C6H3)4. They are highly active olefin metathesis catalysts, allowing for turnover numbers up to 10,000 in various olefin metathesis reactions including alkenes bearing nitrile, sec-amine, and thioether groups. PMID:25938340

  14. GEOMETRY AND ELECTRONIC STRUCTURE OF (CO)3N1CH2. A MODEL TRANSITION METAL CARBENE

    SciTech Connect

    Spangler, Dale; Wendoloski, John J.; Dupuis, Michel; Chen, Maynard M.L.; Schaefer III, Henry F.

    1980-04-01

    The first application of nonempirical molecular electronic structure theory to a realistic transition metal carbene complex is reported. The system chosen was (CO){sub 3}NiCH{sub 2}, methylene (tricarbonyl) nickel(0). All studies were carried out at the self-consistent-field (SCF) level. A large and flexibly contracted basis set was chosen, labeled Ni(15s 11p 6d/11s 8p 3d); C,O(9s 5p/4s 2p); H(5s/3s). In addition, the importance of methylene carbon d functions was investigated. The critical predicted equilibrium geometrical parameters were R [Ni-C (methylene)]=1.83 {Angstrom}, {theta}(HCH)=108°. The sixfold barrier to rotation about the Ni-C (methylene) axis is small, ~o.2 kcal. The electronic structure of (CO){sub 3}NiCH{sub 2} is discussed and compared with those of the "naked" complex NiCH{sub 2} and the stable Ni(CO){sub 4} molecule.

  15. Reactivity of electropositive f-block metal N-heterocyclic carbene complexes 

    E-print Network

    Germeroth, Anne Inger

    2013-06-29

    The combination of Lewis acidic f-block metals and a labile nucleophilic carbene can be an excellent means to activate small molecules such as silanes, CO2 and other traditionally inert substrates. Furthermore, bidentate ...

  16. Gold-Catalyzed Reactions via Cyclopropyl Gold Carbene-like Intermediates

    PubMed Central

    2015-01-01

    Cycloisomerizations of 1,n-enynes catalyzed by gold(I) proceed via electrophilic species with a highly distorted cyclopropyl gold(I) carbene-like structure, which can react with different nucleophiles to form a wide variety of products by attack at the cyclopropane or the carbene carbons. Particularly important are reactions in which the gold(I) carbene reacts with alkenes to form cyclopropanes either intra- or intermolecularly. In the absence of nucleophiles, 1,n-enynes lead to a variety of cycloisomerized products including those resulting from skeletal rearrangements. Reactions proceeding through cyclopropyl gold(I) carbene-like intermediates are ideally suited for the bioinspired synthesis of terpenoid natural products by the selective activation of the alkyne in highly functionalized enynes or polyenynes. PMID:26061916

  17. Synthetic and catalytic studies of Group 11 N-heterocyclic carbene complexes

    E-print Network

    Laitar, David S. (David Stephen)

    2006-01-01

    This thesis presents the synthesis, structure and reactivity of two-coordinate Group 11 metal complexes, supported by N-heterocyclic carbene (NHC) ligands. The NHC ligand was found to stabilize monomeric, terminal fluoride ...

  18. Small molecule activation using electropositive metal N-heterocyclic carbene complexes 

    E-print Network

    Turner, Zoe Rose

    2011-06-27

    The versatility of N-heterocyclic carbenes (NHCs) is demonstrated by numerous practical applications in homogeneous transition metal catalysis, organocatalysis and materials science. There remains a paucity of electropositive ...

  19. Quantitative description of structural effects on the stability of gold(I) carbenes.

    PubMed

    Ringger, David H; Kobylianskii, Ilia J; Serra, Daniel; Chen, Peter

    2014-10-27

    The gas-phase bond-dissociation energies of a SO2 -imidazolylidene leaving group of three gold(I) benzyl imidazolium sulfone complexes are reported (E0 =46.6±1.7, 49.6±1.7, and 48.9±2.1?kcal?mol(-1) ). Although these energies are similar to each other, they are reproducibly distinguishable. The energy-resolved collision-induced dissociation experiments of the three [L]-gold(I) (L=ligand) carbene precursor complexes were performed by using a modified tandem mass spectrometer. The measurements quantitatively describe the structural and electronic effects a p-methoxy substituent on the benzyl fragment, and trans [NHC] and [P] gold ligands, have towards gold carbene formation. Evidence for the formation of the electrophilic gold carbene in solution was obtained through the stoichiometric and catalytic cyclopropanation of olefins under thermal conditions. The observed cyclopropane yields are dependent on the rate of gold carbene formation, which in turn is influenced by the ligand and substituent. The donation of electron density to the carbene carbon by the p-methoxy benzyl substituent and [NHC] ligand stabilizes the gold carbene intermediate and lowers the dissociation barrier. Through the careful comparison of gas-phase and solution chemistry, the results suggest that even gas-phase leaving-group bond-dissociation energy differences of 2-3?kcal?mol(-1) enormously affect the rate of gold carbene formation in solution, especially when there are competing reactions. The thermal decay of the gold carbene precursor complex was observed to follow first-order kinetics, whereas cyclopropanation was found to follow pseudo-first-order kinetics. Density-functional-theory calculations at the M06-L and BP86-D3 levels of theory were used to confirm the observed gas-phase reactivity and model the measured bond-dissociation energies. PMID:25236486

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

    PubMed Central

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

    2011-01-01

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

  1. Stabilization of fully reduced iron-sulfur clusters by carbene ligation: the [FenSn]0 oxidation levels (n = 4, 8).

    PubMed

    Deng, Liang; Holm, R H

    2008-07-30

    The all-ferrous [Fe4S4](0) state has been demonstrated in the fully reduced Fe protein of the Azotobacter vinelandii nitrogenase complex. We seek synthetic analogues of this state more tractable than the recently prepared but highly unstable cluster [Fe4S4(CN)4](4-) (Scott, Berlinguette, Holm, and Zhou, Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 9741). The N-heterocyclic carbene 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (Pr(i)2NHCMe2) has been found to stabilize the fully reduced clusters [Fe8S8(Pr(i)2NHCMe2)6] (4) and [Fe4S4(Pr(i)2NHCMe2)4] (5), which are prepared by cluster assembly or phosphine substitution of FenSn (n = 8, 16) clusters. Cluster 4 is also obtained by reaction of the carbene with all-ferrous [Fe7S6(PEt3)5Cl2] (3) and cluster 5 by carbene cleavage of 4. Detailed structures of 3 (monocapped prismatic), 4, and 5 are described; the latter two are the first iron-sulfur clusters with Fe-C sigma bonds. Cluster 4 possesses the [Fe8(mu3-S) 6(mu4-S)2] edge-bridged double cubane structure and 5 the cubane-type [Fe4(mu3-S)4] stereochemistry. The all-ferrous formulations of the clusters are confirmed by X-ray structure parameters and (57)Fe isomer shifts. Both clusters are stable under conventional aprotic anaerobic conditions, enabling further study of reactivity. The collective properties of 5 indicate that it is a meaningful synthetic analogue of the core of the fully reduced protein-bound cluster. PMID:18593124

  2. N-Heterocyclic Carbene Complexes in Reactions Involving Carbon Monoxide

    NASA Astrophysics Data System (ADS)

    Jeletic, Matthew; Veige, Adam

    This chapter focuses on carbon monoxide as a reagent in M-NHC catalysed reactions. The most important and popular of these reactions is hydroformylation. Unfortunately, uncertainty exists as to the identity of the active catalyst and whether the NHC is bound to the catalyst in a number of the reported reactions. Mixed bidentate NHC complexes and cobalt-based complexes provide for better stability of the catalyst. Catalysts used for hydroaminomethylation and carbonylation reactions show promise to rival traditional phosphine-based catalysts. Reports of decarbonylation are scarce, but the potential strength of the M-NHC bond is conducive to the harsh conditions required. This report will highlight, where appropriate, the potential benefits of exchanging traditional phosphorous ligands with N-heterocyclic carbenes as well as cases where the role of the NHC might need re-evaluation. A review by the author on this topic has recently appeared [1].

  3. How Stable Is Stable?

    ERIC Educational Resources Information Center

    Baehr, Marie

    1994-01-01

    Provides a problem where students are asked to find the point at which a soda can floating in some liquid changes its equilibrium between stable and unstable as the soda is removed from the can. Requires use of Newton's first law, center of mass, Archimedes' principle, stable and unstable equilibrium, and buoyant force position. (MVL)

  4. Synthesis of the first radiolabeled 188Re N-heterocyclic carbene complex and initial studies on its potential use in radiopharmaceutical applications.

    PubMed

    Wagner, Thomas; Zeglis, Brian M; Groveman, Sam; Hille, Claudia; Pöthig, Alexander; Francesconi, Lynn C; Herrmann, Wolfgang A; Kühn, Fritz E; Reiner, Thomas

    2014-06-15

    A novel approach towards the synthesis of radiolabeled organometallic rhenium complexes is presented. We successfully synthesized and analyzed the first (188)Re-labeled N-heterocyclic biscarbene complex, trans-dioxobis(1,1'-methylene-bis(3,3'-diisopropylimidazolium-2-ylidene))(188)rhenium(V) hexafluorophosphate ((188)Re-4) via transmetalation using an air-stable and moisture-stable silver(I) biscarbene complex. In order to assess the viability of this complex as a potential lead structure for in vivo applications, the stability of the (188)Re-NHC complex was tested in physiologically relevant media. Ultimately, our studies illustrate that the complex we synthesized dissociates rapidly and is therefore unsuitable for use in radiopharmaceuticals. However, it is clear that the transmetalation approach we have developed is a rapid, robust, and mild method for the synthesis of new (188)Re-labeled carbene complexes. PMID:24889257

  5. Synthesis of the first radiolabeled 188Re N-heterocyclic carbene complex and initial studies on its potential use in radiopharmaceutical applications

    PubMed Central

    Wagner, Thomas; Zeglis, Brian M.; Groveman, Sam; Hille, Claudia; Pöthig, Alexander; Francesconi, Lynn C.; Herrmann, Wolfgang A.; Kühn, Fritz E.; Reiner, Thomas

    2015-01-01

    A novel approach towards the synthesis of radiolabeled organometallic rhenium complexes is presented. We successfully synthesized and analyzed the first 188Re-labeled N-heterocyclic biscarbene complex, trans-dioxobis(1,1?-methylene-bis(3,3?-diisopropylimidazolium-2-ylidene))188rhenium(V) hexafluorophosphate (188Re-4) via transmetalation using an air-stable and moisture-stable silver(I) biscarbene complex. In order to assess the viability of this complex as a potential lead structure for in vivo applications, the stability of the 188Re-NHC complex was tested in physiologically relevant media. Ultimately, our studies illustrate that the complex we synthesized dissociates rapidly and is therefore unsuitable for use in radiopharmaceuticals. However, it is clear that the transmetalation approach we have developed is a rapid, robust, and mild method for the synthesis of new 188Re-labeled carbene complexes. PMID:24889257

  6. Effect of substituents at the heteroatom on the structure and ligating properties of heterocyclic carbene, silylene, germylene and abnormal carbene: a theoretical study.

    PubMed

    Guha, Ankur Kanti; Sarmah, Satyajit; Phukan, Ashwini K

    2010-08-21

    The effect of substituents at the heteroatom on the electronic structures of different N-heterocyclic carbenes (1, 2 and 3), silylene (4) and germylene (5) are examined using Density Functional Theory. The kinetic and thermodynamic stabilities of these molecules are assessed by examining the HOMO-LUMO gap and hydrogenation energies, respectively. The extent of cyclic electron delocalization present in these five-membered ring systems are quantified with the help of NICS calculations. The ligating properties of 1-5 and the recently synthesized free abnormal carbene 6 (Bertrand et al., Science, 2009, 326, 556-559) are examined by looking at the energies of the sigma symmetric electron-donating orbital of the respective molecules. Among the systems considered, 6 is found to have the strongest sigma-donating ability. A comparative study of the ligating properties between the two isomeric carbenes 1 and 6 is performed by calculating the carbonyl stretching frequencies of some iridium carbonyl complexes of these two tautomeric carbenes. PMID:20607170

  7. The influence of anionic ligands on stereoisomerism of Ru carbenes and their importance to efficiency and selectivity of catalytic olefin metathesis reactions.

    PubMed

    Torker, Sebastian; Khan, R Kashif M; Hoveyda, Amir H

    2014-03-01

    Investigations detailed herein provide insight regarding the mechanism of stereochemical inversion of stereogenic-at-Ru carbene complexes through a nonolefin metathesis-based polytopal rearrangement pathway. Computational analyses (DFT) reveal that there are two key factors that generate sufficient energy barriers that are responsible for the possibility of isolation and characterization of high-energy, but kinetically stable, intermediates: (1) donor-donor interactions that involve the anionic ligands and the strongly electron donating carbene groups and (2) dipolar effects arising from the syn relationship between the anionic groups (iodide and phenoxide). We demonstrate that a Brønsted acid lowers barriers to facilitate isomerization, and that the positive influence of a proton source is the result of its ability to diminish the repulsive electronic interactions originating from the anionic ligands. The implications of the present studies regarding a more sophisticated knowledge of the role of anionic units on the efficiency of Ru-catalyzed olefin metathesis reactions are discussed. The electronic basis for the increased facility with which allylic alcohols participate in olefin metathesis processes will be presented as well. Finally, we illustrate how a better understanding of the role of anionic ligands has served as the basis for successful design of Ru-based Z-selective catalysts for alkene metathesis. PMID:24533571

  8. A Non-Diazo Approach to ?-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation

    PubMed Central

    2015-01-01

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, ?-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C–H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate ?-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous ?-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile ?-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of ?-oxo gold carbene intermediates. The intermolecular approach offers excellent synthetic flexibility because no tethering of the oxidant is required, and its reduced form is not tangled with the product. We were the first research group to develop this strategy, through the use of pyridine/quinolone N-oxides as the external oxidants. In this manner, we can effectively make a C–C triple bond a surrogate of an ?-diazo carbonyl moiety in various gold catalyses. With terminal alkynes, we demonstrated that we can efficiently trap exclusively formed terminal carbene centers by internal nucleophiles en route to the formation of cyclic products, including strained oxetan-3-ones and azetidin-3-ones, and by external nucleophiles when a P,N-bidentate ligand is coordinated to gold. With internal alkynes, we generated synthetically useful regioselectivities in the generation of the ?-oxo gold carbene moiety, which enables expedient formation of versatile enone products. Other research groups have also applied this strategy en route to versatile synthetic methods. The ?-oxo gold carbenes appear to be more electrophilic than their Rh counterpart, which many chemists have focused on in a large array of excellent work on metal carbene chemistry. The ease of accessing the reactive gold carbenes opens up a vast area for developing new synthetic methods that would be distinctively different from the known Rh chemistry and promises to generate a new round of “gold rush”. PMID:24428596

  9. A non-diazo approach to ?-oxo gold carbenes via gold-catalyzed alkyne oxidation.

    PubMed

    Zhang, Liming

    2014-03-18

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, ?-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C-H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate ?-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous ?-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile ?-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of ?-oxo gold carbene intermediates. The intermolecular approach offers excellent synthetic flexibility because no tethering of the oxidant is required, and its reduced form is not tangled with the product. We were the first research group to develop this strategy, through the use of pyridine/quinolone N-oxides as the external oxidants. In this manner, we can effectively make a C-C triple bond a surrogate of an ?-diazo carbonyl moiety in various gold catalyses. With terminal alkynes, we demonstrated that we can efficiently trap exclusively formed terminal carbene centers by internal nucleophiles en route to the formation of cyclic products, including strained oxetan-3-ones and azetidin-3-ones, and by external nucleophiles when a P,N-bidentate ligand is coordinated to gold. With internal alkynes, we generated synthetically useful regioselectivities in the generation of the ?-oxo gold carbene moiety, which enables expedient formation of versatile enone products. Other research groups have also applied this strategy en route to versatile synthetic methods. The ?-oxo gold carbenes appear to be more electrophilic than their Rh counterpart, which many chemists have focused on in a large array of excellent work on metal carbene chemistry. The ease of accessing the reactive gold carbenes opens up a vast area for developing new synthetic methods that would be distinctively different from the known Rh chemistry and promises to generate a new round of "gold rush". PMID:24428596

  10. A Continuum of Progress: Applications of N-Hetereocyclic Carbene Catalysis in Total Synthesis

    PubMed Central

    Izquierdo, Javier; Hutson, Gerri E.; Cohen, Daniel T.; Scheidt, Karl A.

    2013-01-01

    N-Heterocyclic carbene (NHC) catalyzed transformations have emerged as powerful tactics for the construction of complex molecules. Since Stetter’s report in 1975 of the total synthesis of cis-jasmon and dihydrojasmon by using carbene catalysis, the use of NHCs in total synthesis has grown rapidly, particularly over the last decade. This renaissance is undoubtedly due to the recent developments in NHC-catalyzed reactions, including new benzoin, Stetter, homoenolate, and aroylation processes. These transformations employ typical as well as Umpolung types of bond disconnections and have served as the key step in several new total syntheses. This Minireview highlights these reports and captures the excitement and emerging synthetic utility of carbene catalysis in total synthesis. PMID:23074146

  11. Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

    PubMed Central

    Cotugno, Pietro; Zambonin, Carlo Giorgio; Ciminale, Francesco

    2015-01-01

    Summary The Pd–benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji–Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand is also proposed. PMID:26199653

  12. Olefin Metathesis With Ruthenium-Arene Catalysts Bearing N-Heterocyclic Carbene Ligands

    NASA Astrophysics Data System (ADS)

    Delaude, Lionel; Demonceau, Albert

    In this chapter, we summarize the main results of our investigations on the ring-opening metathesis polymerization (ROMP) of cyclooctene catalyzed by various ruthenium (Ru)-arene complexes bearing imidazolin-2-ylidene, imidazolidin- 2-ylidene, or triazolin-5-ylidene ligands. Three major findings emerged from this study. First, we underscored the intervention of a photochemical activation step due to visible light illumination. Second, we established that the presence of an endocyclic double bond in the carbene ligand central heterocycle was not crucial to achieve high catalytic efficiencies. Third, we demonstrated that ortho-metallation of the N-heterocyclic carbene (NHC) ligand by the Ru center led to inactive catalysts.

  13. Gold(I) Carbenes by Retro-Buchner Reaction: Generation and Fate

    PubMed Central

    2013-01-01

    The fate of the aryl gold(I) carbenes generated by retro-Buchner reaction of ortho-substituted 7-aryl-1,3,5-cycloheptatrienes is dependent on the constitution of the ortho substituent. Indenes and fluorenes are obtained by intramolecular reaction of highly electrophilic gold(I) carbenes with alkenes and arenes. According to density functional theory calculations, the gold-catalyzed retro-Buchner process occurs stepwise, although the two carbon–carbon cleavages occur on a rather flat potential energy surface. PMID:24358986

  14. A Desulfonylative Approach in Oxidative Gold Catalysis: Regiospecific Access to Donor-Substituted Acyl Gold Carbenes.

    PubMed

    Chen, Hongyi; Zhang, Liming

    2015-09-28

    Donor-substituted acyl gold carbenes are challenging to access selectively by gold-promoted intermolecular oxidation of internal alkynes as the opposite regioisomers frequently predominate. By using alkynyl sulfones or sulfonates as substrates, the oxidative gold catalysis in the presence of substituted pyridine N-oxides offers regiospecific access to acyl/aryl, acyl/alkenyl, and acyl/alkoxy gold carbenes by in?situ expulsion of sulfur dioxide. The intermediacies of these reactive species are established by their reactivities, including undergoing further oxidation by the same oxidant, cyclopropanation of styrenes, engaging in a [3+2] cycloaddition with ?-methylstyrene, and conversion into dienones. PMID:26266676

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

    PubMed

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

    2015-12-22

    New ruthenium Grubbs' and Hoveyda-Grubbs' second generation catalysts bearing N-alkyl/N-isopropylphenyl N-heterocyclic carbene (NHC) ligands with syn or anti backbone configuration were obtained and compared in model olefin metathesis reactions. Different catalytic efficiencies were observed depending on the size of the N-alkyl group (methyl or cyclohexyl) and on the backbone configuration. The presence of an N-cyclohexyl substituent determined the most significant reactivity differences between catalysts with syn or anti phenyl groups on the backbone. In particular, anti catalysts proved highly efficient, especially in the ring-closing metathesis (RCM) of encumbered diolefins, while syn catalysts showed low efficiency in the RCM of less hindered diolefins. This peculiar behavior, rationalized through DFT studies, was found to be related to the high propensity of these catalysts to give nonproductive metathesis events. Enantiopure anti catalysts were also tested in asymmetric metathesis reactions, where moderate enantioselectivities were observed. The steric and electronic properties of unsymmetrical NHCs with the N-cyclohexyl group were then evaluated using the corresponding rhodium complexes. While steric factors proved unimportant for both syn and anti NHCs, a major electron-donating character was found for the unsymmetrical NHC with anti phenyl substituents on the backbone. PMID:26608162

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

    NASA Astrophysics Data System (ADS)

    Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

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

  17. C4 cumulene and the corresponding air-stable radical cation and dication.

    PubMed

    Li, Yan; Mondal, Kartik Chandra; Samuel, Prinson P; Zhu, Hongping; Orben, Claudia M; Panneerselvam, Saravanan; Dittrich, Birger; Schwederski, Brigitte; Kaim, Wolfgang; Mondal, Totan; Koley, Debasis; Roesky, Herbert W

    2014-04-14

    A neutral C4 cumulene 1 that includes a cyclic alkyl(amino) carbene (cAAC), its air-stable radical cation 1(·+) , and dication 1(2+) have been synthesized. The redox property of 1(·+) was studied by cyclic voltammetry. EPR and theoretical calculations show that the unpaired electron in 1(·+) is mainly delocalized over the central C4 backbone. The commercially available CBr4 is utilized as a source of dicarbon in the cumulene synthesis. PMID:24623450

  18. 1,2-Migration in Rhodium(II) Carbene Transfer Reaction: Remarkable Steric Effect on

    E-print Network

    Wang, Jianbo

    nonmigrating (bystander) effect has been observed. For example, the 1,2-aryl migration becomes completely origin (Scheme 1).4d This effect of the bystander has been attributed to their electronic effects1,2-Migration in Rhodium(II) Carbene Transfer Reaction: Remarkable Steric Effect on Migratory

  19. Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations.

    PubMed

    Li, Xiaoxun; Li, Hui; Song, Wangze; Tseng, Po-Sen; Liu, Lingyan; Guzei, Ilia A; Tang, Weiping

    2015-10-26

    Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed. PMID:26480329

  20. Nitrogen heterocyclic carbene containing pentacoordinate iron dicarbonyl as a [Fe]-hydrogenase active site model.

    PubMed

    Jiang, Shuang; Zhang, Tianyong; Zhang, Xia; Zhang, Guanghui; Li, Bin

    2015-10-14

    A novel pentacoordinate mono iron dicarbonyl complex bearing a nitrogen heterocyclic carbene ligand was reported as a model of a [Fe]-hydrogenase active site, which exhibits interesting proton coupled CO binding reactivity, electro-catalytic proton reduction and catalytic transfer hydrogenation reactivity. PMID:26369379

  1. Mesoionic Carbene-Gold(I) Catalyzed Bis-Hydrohydrazination of Alkynes with Parent Hydrazine.

    PubMed

    Tolentino, Daniel R; Jin, Liqun; Melaimi, Mohand; Bertrand, Guy

    2015-10-01

    A novel synthetic route gives access to mesoionic carbene and cyclopropenylidene supported gold chloride complexes. The corresponding cationic MIC-gold complex obtained by chloride abstraction allows for the first transition metal-catalyzed functionalization of both nitrogens of parent hydrazine. PMID:25597889

  2. A comparison of the bonding in the second-row transition-metal oxides and carbenes

    NASA Astrophysics Data System (ADS)

    Siegbahn, Per E. M.

    1993-01-01

    Calculations including electron correlation of all valence electrons have been performed for the sequence of second-row transition-metal oxides and carbenes. For the atoms to the right the bond strengths of the carbenes and the oxides are similar while for the atoms to the left the oxide bond strengths are much larger. The origin of this difference is the interaction between the oxygen lone pairs and empty 4d orbitals on the metal. With the large donation of electrons from the oxygen lone pair to the metal for the atoms to the left, the bonding can almost be described as triple bond formation for YO, ZrO and NbO. For MoO, where a 4d ? orbital is singly occupied on the metal, the bond strength is much smaller than for the oxides to the left. For the metal carbenes two covalent bonds are formed. The ground state spin for the oxides to the right is higher than for the corresponding carbenes, which can be explained by the presence of the ? degeneracy for the oxides. The relevance of the present results for the epoxidation and the olefin metathesis reactions are discussed.

  3. Vinyl dihydropyrans and dihydrooxazines: cyclizations of catalytic ruthenium carbenes derived from alkynals and alkynones.

    PubMed

    Cambeiro, Fermín; López, Susana; Varela, Jesús A; Saá, Carlos

    2014-06-01

    A novel synthesis of 2-vinyldihydropyrans and dihydro-1,4-oxazines (morpholine derivatives) from alkynals and alkynones has been developed. The cyclizations require a mild generation of catalytic ruthenium carbenes from terminal alkynes and (trimethylsilyl)diazomethane followed by trapping with carbonyl nucleophiles. Mechanistic aspects of the new cyclizations are discussed. PMID:24798093

  4. Influence of bulky yet flexible N-heterocyclic carbene ligands in gold catalysis

    PubMed Central

    Collado, Alba; Patrick, Scott R; Gasperini, Danila; Meiries, Sebastien

    2015-01-01

    Summary Three new Au(I) complexes of the formula [Au(NHC)(NTf2)] (NHC = N-heterocyclic carbene) bearing bulky and flexible ligands have been synthesised. The ligands studied are IPent, IHept and INon which belong to the ‘ITent’ (‘Tent’ for ‘tentacular’) family of NHC derivatives. The effect of these ligands in gold-promoted transformations has been investigated. PMID:26664600

  5. Rhodium(I) N-Heterocyclic Carbene Bioorganometallics as in Vitro Antiproliferative Agents with Distinct Effects on Cellular Signaling.

    PubMed

    Oehninger, Luciano; Spreckelmeyer, Sarah; Holenya, Pavlo; Meier, Samuel M; Can, Suzan; Alborzinia, Hamed; Schur, Julia; Keppler, Bernhard K; Wölfl, Stefan; Ott, Ingo

    2015-12-24

    Organometallics with N-heterocyclic carbene (NHC) ligands have triggered major interest in inorganic medicinal chemistry. Complexes of the type Rh(I)(NHC)(COD)X (where X is Cl or I, COD is cyclooctadiene, and NHC is a dimethylbenzimidazolylidene) represent a promising type of new metallodrugs that have been explored by advanced biomedical methods only recently. In this work, we have synthesized and characterized several complexes of this type. As observed by mass spectrometry, these complexes remained stable over at least 3 h in aqueous solution, after which hydrolysis of the halido ligands occurred and release of the NHC ligand was evident. Effects against mitochondria and general cell tumor metabolism were noted at higher concentrations, whereas phosphorylation of HSP27, p38, ERK1/2, FAK, and p70S6K was induced substantially already at lower exposure levels. Regarding the antiproliferative activity in tumor cells, a clear preference for iodido over chlorido secondary ligands was noted, as well as effects of the substituents of the NHC ligand. PMID:26595649

  6. Intermolecular Reactions of a Foiled Carbene with Carbonyl Compounds: The Effects of Trishomocyclopropyl Stabilization.

    PubMed

    Apeland, Ingrid Malene; Rosenberg, Murray G; Arion, Vladimir B; Kählig, Hanspeter; Brinker, Udo H

    2015-12-01

    endo-Tricyclo[3.2.1.0(2,4)]oct-8-ylidene is a foiled carbene reaction intermediate. It was generated by thermolyzing ?(3)-1,3,4-oxadiazoline precursors dissolved in benzaldehyde and acetophenone. The products appear to stem from direct insertion of the carbene's divalent C atom into the ?-bonds of the carbonyl compounds; however, this is only superficial. The strict stereochemistry observed is due to the topologies of the reaction intermediates of the proposed two-step mechanism. Bimolecular nucleophilic addition generates bent 1,3-zwitterions. The neutral reaction intermediates undergo pinacolic rearrangements to form the observed adducts. Product ratios reflect the migratory aptitudes of the carbonyl compounds' ?-substituents. The carbene reaction was modeled using DFT. The singlet carbene's bicoordinate C atom bends 31° toward the endo-fused cyclopropane bond, elongating it to r = 1.69 Å. The resulting trishomocyclopropyl HOMO{-1} is a three-center two-electron bond responsible for the electron-deficient carbene's nucleophilicity. Its calculated properties are consistent with this assertion: (1) singlet-triplet (?ES-T) energy gap of -25 kcal/mol, (2) gas-phase proton affinity (PA) value of 272 kcal/mol, (3) hard and soft acid and base (HSAB) ?N value of -0.2 in its initial reaction with the carbonyl compounds, and (4) negative frontier orbital interaction values ??E(PhC(O)H) = -4.38 eV and ??E(PhC(O)Me) = -3.97 eV. PMID:26447842

  7. Formation of Ruthenium Carbenes by gem-Hydrogen Transfer to Internal Alkynes: Implications for Alkyne trans-Hydrogenation

    PubMed Central

    Leutzsch, Markus; Wolf, Larry M; Gupta, Puneet; Fuchs, Michael; Thiel, Walter; Farès, Christophe; Fürstner, Alois

    2015-01-01

    Insights into the mechanism of the unusual trans-hydrogenation of internal alkynes catalyzed by {Cp*Ru} complexes were gained by para-hydrogen (p-H2) induced polarization (PHIP) transfer NMR spectroscopy. It was found that the productive trans-reduction competes with a pathway in which both H atoms of H2 are delivered to a single alkyne C atom of the substrate while the second alkyne C atom is converted into a metal carbene. This “geminal hydrogenation” mode seems unprecedented; it was independently confirmed by the isolation and structural characterization of a ruthenium carbene complex stabilized by secondary inter-ligand interactions. A detailed DFT study shows that the trans alkene and the carbene complex originate from a common metallacyclopropene intermediate. Furthermore, the computational analysis and the PHIP NMR data concur in that the metal carbene is the major gateway to olefin isomerization and over-reduction, which frequently interfere with regular alkyne trans-hydrogenation. PMID:26332643

  8. The Real Role of N-Heterocyclic Carbene in Reductive Functionalization of CO2: An Alternative Understanding from Density Functional Theory Study.

    PubMed

    Zhou, Qinghai; Li, Yuxue

    2015-08-19

    The mechanisms of reductive functionalization of CO2 to formamide catalyzed by N-heterocyclic carbene (NHC) were comprehensively studied with DFT calculations. New activation mode with much lower energy barrier than those proposed before was discovered. In this reaction, NHC acts as neither a CO2 nor a silane activator, but as a precursor of the real catalyst, i.e., the in situ formed ionic liquid [NHCH](+)[Carbamate](-). In this loose contact ion pair, the negatively charged O atom of the carbamate anion becomes the new active site and is free to do nucleophilic attack. When amine is absent, CO2 will be converted into methanol. In this case, the NHC-CO2 adduct is the real catalytic species, the active site shifted from the carbene C atom to the negatively charged O atom. These new activation modes follow a pattern of "S(N)2@Si-Acceptor", in which the Si-H bond is activated via concerted backside S(N)2 nucleophilic attack by the negatively charged O atom, and the leaving hydride is directly accepted by a free CO2 molecule. The advantages of these new activation modes originate from the following points: (1) The ionic liquid [NHCH](+)[Carbamate](-) and NHC-CO2 adduct are thermodynamically more stable than NHC. (2) The active site of the NHC catalyst is extended outside a lot. Consequently, the large steric effect between the NHC arms and the substrates in transition state can be avoided to some extent. (3) The O atom has good silicon affinity. In addition, a free CO2 molecule, whose carbon atom is more electrophilic than those of the CO2 moieties in NHC-CO2 adduct and carbamate, acts as an efficient hydride acceptor. PMID:26220202

  9. Dynamic Behavior of N-Heterocyclic Carbene Boranes: Boron-Carbene Bonds in B,B-Disubstituted N,N-Dimethylimidazol-2-ylidene Boranes Have Substantial Rotation Barriers.

    PubMed

    Damodaran, Krishnan; Li, Xiben; Pan, Xiangcheng; Curran, Dennis P

    2015-05-01

    Dynamic NMR spectroscopy has been used to measure rotation barriers in five B,B-disubstituted 1,3-dimethylimidazol-2-ylidene boranes. The barriers are attributed to the sp(2)-sp(3) bond between C(1) of the N-heterocyclic carbene ring and the boron atom. Bonds to boron atoms bearing a thexyl (1,1,2-trimethylpropyl) group show especially high barriers, ranging from 75-86 kJ mol(-1). 2-Isopropyl-1,3,5-trimethylbenzene is used as a comparable to help understand the nature and magnitude of the barriers. PMID:25843519

  10. Cationic rhenium complexes ligated with N-heterocyclic carbenes - an overview.

    PubMed

    Hille, Claudia; Kühn, Fritz E

    2015-12-14

    This review provides an overview of the currently known cationic rhenium NHC complexes. Synthesis, structures and properties are described. The title compounds are potential candidates for both catalytic and medical applications. Besides the variety of ancillary ligands, which are in some cases easily substituted, functionalization can be carried out in the side chain or at the backbone of the carbene ligand as well as - in the case of biscarbene ligands - at the bridging moiety. Cationic Re NHC complexes are promising precursors for radiopharmaceuticals and diagnostics - not only because of the possibility to radiolabel the metal (steps in this direction have been made and described already) - but rather the opportunity to link the complexes to biomolecules via the different possibilities provided by the ligands. The development of OLEDs based on luminescent Re(i) carbene complexes renders another potential application. PMID:26587970

  11. An Isolable, Photoswitchable N-Heterocyclic Carbene: On-Demand Reversible Ammonia Activation.

    PubMed

    Teator, Aaron J; Tian, Yuan; Chen, Mu; Lee, Jeehiun K; Bielawski, Christopher W

    2015-09-21

    The first isolable, photoswitchable N-heterocyclic carbene was synthesized and found to undergo reversible electrocyclic isomerization upon successive exposure to UV and visible radiation. The UV-induced ring closure afforded substantial changes to the electronic structure of the dithienylethene-based NHC, as evidenced by changes in the corresponding UV/Vis absorption and (13) C?NMR spectra. Likewise, molecular orbital calculations revealed diminished electron density at the carbene nucleus upon photocyclization, consistent with the enhanced electrophilicity displayed by the ring-closed form. The photoswitchable NHC was successfully switched between its ring-opened and ring-closed states with high fidelity over multiple cycles. Furthermore, the ring-closed isomer was found to undergo facile N?H bond activation, allowing for the controlled capture and release of ammonia upon cycling between its isomeric states. PMID:26274507

  12. Synthesis, characterization and catalytic activity of saturated and unsaturated N-heterocyclic carbene iridium(i) complexes.

    PubMed

    Chang, Yung-Hung; Fu, Ching-Feng; Liu, Yi-Hong; Peng, Shei-Ming; Chen, Jwu-Ting; Liu, Shiuh-Tzung

    2009-02-01

    Both saturated and unsaturated N-benzyl substituted heterocyclic carbene (NHC) iridum(i) complexes were synthesized. The unsaturated carbene complex [(un-NHC-Bn)Ir(CO)(2)Cl] in the cis form was prepared via the carbene transfer from the corresponding silver complex to [Ir(COD)(2)Cl](2) followed by ligand substitution with CO, whereas the saturated complex was obtained via the transfer from (sat-NHC-Bn)W(CO)(5). The treatment of phosphines with (NHC)Ir(CO)(2)Cl complexes yielded the products with the phosphine ligand trans to the carbene moiety via substitution. X-Ray structural determination shows that distances of Ir-C((carbene)) in both (un-NHC-Bn)Ir(CO)(PR(3))Cl and (un-NHC-Bn)Ir(CO)(PR(3))Cl are essentially the same. Analyses of spectroscopic and crystal structural data of iridium complexes [(NHC)Ir(CO)(PR(3))Cl] and Vaska's complex show similar corresponding data in both types of complexes, suggesting that the studied NHC ligands and phosphines have similar bonding with Ir(i) metal center. All iridium complexes studied in this work illustrated their catalytically activity on N-alkylation of amine with alcohol via hydrogen transfer reduction. It appears no dramatic difference on the catalytic activity among these iridium carbene complexes; but the saturated carbene complex (sat-NHC-Bn)Ir(CO)(PR(3))Cl appears to be slightly more active. For example, the reaction of benzyl alcohol with aniline in the presence of catalyst (1 mol%) under basic conditions at 100 degrees C provided the secondary amine (N-benzylaniline) in 96% yield. PMID:19156280

  13. Catalytic Dynamic Kinetic Resolutions with N-Heterocyclic Carbenes: Asymmetric Synthesis of Highly Substituted ?-Lactones

    PubMed Central

    Cohen, Daniel T.; Eichman, Chad C.; Phillips, Eric M.; Zarefsky, Emily R.

    2012-01-01

    An N-heterocyclic carbene (NHC)-catalyzed dynamic kinetic resolution of racemic ?-substituted ?-keto esters has been developed. This method relies on the epimerization of an NHC-enol intermediate before subsequent aldol/acylation events. Highly substituted ?-lactones are produced in good yield (50–88%) with good to excellent diastereoselectivity (5:1 to 20:1 dr) and excellent enantioselectivity (up to 99% ee). PMID:22700327

  14. Alkyne-azide cycloaddition catalyzed by silver chloride and "abnormal" silver N-heterocyclic carbene complex.

    PubMed

    Ortega-Arizmendi, Aldo I; Aldeco-Pérez, Eugenia; Cuevas-Yañez, Erick

    2013-01-01

    A library of 1,2,3-triazoles was synthesized from diverse alkynes and azides using catalytic amounts of silver chloride instead of copper compounds. In addition, a novel "abnormal" silver N-heterocyclic carbene complex was tested as catalyst in this process. The results suggest that the reaction requires only 0.5% of silver complex, affording 1,2,3-triazoles in good yields. PMID:24307866

  15. Alkyne-Azide Cycloaddition Catalyzed by Silver Chloride and “Abnormal” Silver N-Heterocyclic Carbene Complex

    PubMed Central

    Ortega-Arizmendi, Aldo I.; Aldeco-Pérez, Eugenia; Cuevas-Yañez, Erick

    2013-01-01

    A library of 1,2,3-triazoles was synthesized from diverse alkynes and azides using catalytic amounts of silver chloride instead of copper compounds. In addition, a novel “abnormal” silver N-heterocyclic carbene complex was tested as catalyst in this process. The results suggest that the reaction requires only 0.5% of silver complex, affording 1,2,3-triazoles in good yields. PMID:24307866

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

    PubMed

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

    2014-10-01

    The Grubbs-Hoveyda ruthenium-carbene complex has been covalently immobilized on ionic magnetic nanoparticles utilizing an imidazolium salt linker. The supported catalyst exhibited excellent catalytic activity for ring-closing metathesis (RCM) and cross-metathesis (CM) in the presence of less than 1 mol % of ruthenium. The catalysts can easily be recovered magnetically and reused up to seven times with minimal leaching of ruthenium species. PMID:25215600

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

    NASA Astrophysics Data System (ADS)

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

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

  18. Unveiling the peculiar hydrogen bonding behavior of solvated N-heterocyclic carbenes.

    PubMed

    Hollóczki, Oldamur

    2016-01-01

    To investigate the hydrogen bonding and its dynamics of N-heterocyclic carbenes (NHCs) in solution, a molecular mechanical force field was fitted for the homologous series of 1,3-dialkylimidazol-2-ylidenes. During the exploration of the potential energy surface of the water/1,3-dimethylimidazol-2-ylidene system, it was observed for the first time that the carbene is prone to interaction with hydrogen bond donor molecules also from the rather unusual "on top" orientation, where the direction of the interplay is perpendicular to the plane of the NHC's ring. The fitting of the force field parameters for imidazol-2-ylidenes was found to be the best in the case of a two-site model, which reproduces not only the strength, but also the direction dependency of hydrogen bonding. With the aid of this tool, curious, hitherto unknown types of hydrogen bonding could be unveiled for NHCs. In the case of non-hydrogen bonding solvents, carbenes tend to form short lived, but structurally influental hydrogen bonds between each other via ring hydrogen atoms and the divalent carbon atoms. The chemically highly important hydrogen bond dynamics of NHCs was found to be facilitated by three center hydrogen bonding, where two alcohol molecules bind to a carbene, which is allowed only by the aforementioned relatively strong interaction between the NHC and the hydrogen bond donor in the "on top" orientation. The latter finding has significant effects on processes that involve this kind of replacement, such as the selective transesterification reactions, and the mechanism of proton exchange on azolium rings. PMID:26592182

  19. NHC?SiCl4 : an ambivalent carbene-transfer reagent.

    PubMed

    Böttcher, Tobias; Steinhauer, Simon; Lewis-Alleyne, Lesley C; Neumann, Beate; Stammler, Hans-Georg; Bassil, Bassem S; Röschenthaler, Gerd-Volker; Hoge, Berthold

    2015-01-01

    The addition of BCl3 to the carbene-transfer reagent NHC?SiCl4 (NHC=1,3-dimethylimidazolidin-2-ylidene) gave the tetra- and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC?SiCl4 served as a transfer reagent for the NHC ligand. The addition of BF3 ?OEt2 , on the other hand, gave NHC?BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C2 F5 )2 SiCl2 was treated with NHC?SiCl4 . In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) were detected with [(C2 F5 )SiCl3 ](-) as counterion. A similar result was already reported for the reaction of NHC?SiCl4 with (C2 F5 )2 SiH2 , which gave [(NHC)2 SiCl2 H][(C2 F5 )SiCl3 ]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC?Si(C2 F5 )2 Cl2 and NHC?Si(C2 F5 )2 ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron-poor silylenes. Furthermore, the reactivity of NHC?SiCl4 towards phosphines is discussed. The carbene complex NHC?PCl3 shows similar reactivity to NHC?SiCl4 , and may even serve as a carbene-transfer reagent as well. PMID:25363673

  20. Theoretical study of the mechanism of the N-heterocyclic carbene-catalyzed cyclotetramerization of acrylates.

    PubMed

    Chang, Dehui; Yang, Qiaoqiao; Li, Meng; Fang, Ran

    2016-01-01

    A theoretical study of the N-heterocyclic carbene (NHC)-catalyzed cyclotetramerization of acrylates forming trisubstituted cyclopentenones indicates a mechanism through a key deoxy-Breslow intermediate generated from one molecule of NHC and two molecules of methyl acrylate (MA). Pathways involving different proton-transfer (? or ?) and the role of a tert-butoxide ( (t) BuO(-)) group were investigated. Graphical abstract TOC. PMID:26696541

  1. A Carbene-Stabilized Gold(I) Fluoride: Synthesis and David S. Laitar, Peter Muller, Thomas G. Gray,* and Joseph P. Sadighi*

    E-print Network

    Müller, Peter

    A Carbene-Stabilized Gold(I) Fluoride: Synthesis and Theory David S. Laitar, Peter Mu¨ller, Thomas, 2005 Summary: The first isolable gold(I) fluoride complex, stabilized by an N-heterocyclic carbene (NHC/d interactions between fluoride and gold(I) and indicate a substantial negative charge on fluorine. Fluoride

  2. Fascinating frontiers of N/O-functionalized N-heterocyclic carbene chemistry: from chemical catalysis to biomedical applications.

    PubMed

    John, Alex; Ghosh, Prasenjit

    2010-08-21

    The in vogue N-heterocyclic carbenes (NHCs) have attracted attention largely for its new found popularity in chemical catalysis and also for displaying promising traits in biomedical applications. The current perspective provides an account of our efforts in exploring the utility of N/O-functionalized N-heterocyclic carbenes in these two areas. On the catalysis front, we have employed the N/O-functionalized N-heterocyclic carbene based precatalysts for the C-C and C-N bond forming reactions like the Suzuki-Miyaura, Sonogashira and Hiyama cross-couplings, the base-free Michael addition, the alkene and alkyne hydroamination reactions and the ring-opening polymerization (ROP) of L-lactides that produce biodegradable polylactide polymers while on the biomedical application front, the anticancer and antimicrobial properties of these N/O-functionalized N-heterocyclic carbene complexes were evaluated. Towards this objective, the N-heterocyclic carbene chemistry of a variety of transition metals like Ag, Au, Ni and Pd has been investigated. PMID:20495733

  3. Spin transitions in bis(amidinato)-N-heterocyclic carbene iron(II) and iron(III) complexes.

    PubMed

    Drake, Jessica L; Kaplan, Hilan Z; Wilding, Matthew J T; Li, Bo; Byers, Jeffery A

    2015-10-14

    In contrast to high spin pyridyl diimine iron(ii) dichloride complexes, analogous bis(amidinato)-N-heterocyclic carbene iron(ii) and iron(iii) complexes demonstrate complex magnetic behaviour. In the solid state, they are best described as intermediate spin complexes at low temperatures that demonstrate gradual spin transitions beginning near or below room temperature. Treating the bis(amidinato)-N-heterocyclic carbene iron(ii) complex with an aryl azide revealed enhanced reactivity compared to analogous complexes supported by pyridyl diimine ligands. PMID:26365530

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

    PubMed

    Rouen, Mathieu; Queval, Pierre; Falivene, Laura; Allard, Jessica; Toupet, Loïc; Crévisy, Christophe; Caijo, Frédéric; Baslé, Olivier; Cavallo, Luigi; Mauduit, Marc

    2014-10-13

    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. PMID:25212827

  5. Electronic spectra of linear HC5H and cumulene carbene H2C5.

    PubMed

    Steglich, Mathias; Fulara, Jan; Maity, Surajit; Nagy, Adam; Maier, John P

    2015-06-28

    The 1(3)?u (-)?X(3)?g (-) transition of linear HC5H (A) has been observed in a neon matrix and gas phase. The assignment is based on mass-selective experiments, extrapolation of previous results of the longer HC2n+1H homologues, and density functional and multi-state CASPT2 theoretical methods. Another band system starting at 303 nm in neon is assigned as the 1(1)A1?X˜(1)A1 transition of the cumulene carbene pentatetraenylidene H2C5 (B). PMID:26133432

  6. N-Heterocyclic Carbene Complexes of Rh: Reaction With Dioxygen Without Oxidation

    SciTech Connect

    Praetorius, J.M.; Allen, D.P.; Wang, R.; Webb, J.D.; Grein, F.; Kennepohl, P.; Crudden, C.M.

    2009-05-21

    The reaction of oxygen with rhodium complexes containing N-heterocyclic carbenes was found to give dioxygen complexes with rare square planar geometries and unusually short O-O bond lengths. Analysis of the bonding in these complexes by Rh L-edge X-ray absorption spectroscopy (XAS), Raman spectroscopy, and DFT calculations provides evidence for a bonding model in which singlet oxygen is bound to a Rh(I) d{sup 8} metal complex, rather than the more common Rh(III) d{sup 6} peroxo species with octahedral geometry and O-O bond lengths in the 1.4-1.5 {angstrom} range.

  7. A two-color fluorogenic carbene complex for tagging olefins via metathesis reaction

    NASA Astrophysics Data System (ADS)

    Wirtz, Marcel; Grüter, Andreas; Heib, Florian; Huch, Volker; Zapp, Josef; Herten, Dirk-Peter; Schmitt, Michael; Jung, Gregor

    2015-12-01

    We describe a fluorogenic ruthenium (II) carbene complex in which the chromophore is directly connected to the metal center. The compound introduces a boron dipyrromethene (BODIPY) moiety into target double bonds by metathesis. Tagging of terminal double bonds is demonstrated on immobilized styrene units on a glass surface. We also show that two compounds with distinguishable fluorescence properties are formed in the model reaction with styrene. The outcome of the metathesis reaction is characterized by 19F-NMR, optical spectroscopy, and, finally, single-molecule trajectories. This labeling scheme, in our perception, is of particular interest in the fields of interfacial science and biorthogonal ligation in combination with super-resolution imaging.

  8. Thermally Stable, Latent Olefin Metathesis Catalysts

    PubMed Central

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

    2011-01-01

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

  9. Pd-N-Heterocyclic Carbene (NHC) Organic Silica: Synthesis and Application in Carbon-Carbon Coupling Reactions

    EPA Science Inventory

    The first Pd-N-heterocyclic carbene (NHC) complex in the form of organic silica was prepared using sol-gel method and its application in Heck and Suzuki reaction were demonstrated. These C-C coupling reactions proceeded efficiently under the influence of microwave irradiation, wi...

  10. What difference one double bond makes: Electronic structure of saturated and unsaturated n-heterocyclic carbene ligands in

    E-print Network

    Baik, Mu-Hyun

    What difference one double bond makes: Electronic structure of saturated and unsaturated n-heterocyclic online 26 September 2006 Abstract N-heterocyclic carbene (NHC) ligands are a versatile and useful class impact of the NHC-ligand by decoupling electronic and steric effects through simplified model N-heterocyclic

  11. 2. Despite the steric protection of the carbene carbon atom, 2c,d undergo coupling reactions

    E-print Network

    Salzberg, Steven

    found applications (9, 28­33) even on a large scale. This work establishes that only a single electron, Stuttgart, 1989). 6. U. H. Brinker, Ed., Advances in Carbene Chemistry (JAI Press, Greenwich, CT, vols. 1) by using phi- and omega-scans. We solved the structure by direct methods, using SHELXS-97 [G. M. Sheldrick

  12. Formation of Ruthenium Carbenes by gem-Hydrogen Transfer to Internal Alkynes: Implications for Alkyne trans-Hydrogenation.

    PubMed

    Leutzsch, Markus; Wolf, Larry M; Gupta, Puneet; Fuchs, Michael; Thiel, Walter; Farès, Christophe; Fürstner, Alois

    2015-10-12

    Insights into the mechanism of the unusual trans-hydrogenation of internal alkynes catalyzed by {Cp*Ru} complexes were gained by para-hydrogen (p-H2 ) induced polarization (PHIP) transfer NMR spectroscopy. It was found that the productive trans-reduction competes with a pathway in which both H?atoms of H2 are delivered to a single alkyne C?atom of the substrate while the second alkyne C?atom is converted into a metal carbene. This "geminal hydrogenation" mode seems unprecedented; it was independently confirmed by the isolation and structural characterization of a ruthenium carbene complex stabilized by secondary inter-ligand interactions. A detailed DFT study shows that the trans alkene and the carbene complex originate from a common metallacyclopropene intermediate. Furthermore, the computational analysis and the PHIP NMR data concur in that the metal carbene is the major gateway to olefin isomerization and over-reduction, which frequently interfere with regular alkyne trans-hydrogenation. PMID:26332643

  13. Optimized Syntheses of Cyclopentadienyl Nickel Chloride Compounds Containing "N"-Heterocyclic Carbene Ligands for Short Laboratory Periods

    ERIC Educational Resources Information Center

    Cooke, Jason; Lightbody, Owen C.

    2011-01-01

    Experiments are described for the preparation of imidazolium chloride precursors to "N"-heterocyclic carbenes and their cyclopentadienyl nickel chloride derivatives. The syntheses have been optimized for second- and third-year undergraduate laboratories that have a maximum programmed length of three hours per week. The experiments are flexible and…

  14. Enantioselective Synthesis of Chromanones Bearing Quaternary Substituted Stereocenters Catalyzed by (1R)-Camphor-Derived N-Heterocyclic Carbenes.

    PubMed

    Rafi?ski, Zbigniew; Kozakiewicz, Anna

    2015-08-01

    A catalytic asymmetric intramolecular crossed-benzoin reaction for the synthesis of chromanones by novel camphor-derived N-heterocyclic carbenes is described. The corresponding chromanones bearing quaternary stereogenic centers were isolated in high yields with high to excellent enantioselectivity. PMID:26161638

  15. Cyclopentadiene Construction via Rh-Catalyzed Carbene/Alkyne Metathesis Terminated with Intramolecular Formal [3 + 2] Cycloaddition.

    PubMed

    Zheng, Yang; Mao, Jincheng; Weng, Yuecheng; Zhang, Xiaolu; Xu, Xinfang

    2015-11-20

    A new type of intramolecular carbene cascade reaction of alkynyl-tethered styryl diazoesters is presented, which is terminated with a formal [3 + 2] cycloaddition to give the bicyclic cyclopentadiene derivatives in high yields and selectivity. Additionally, it was found that the ?-H shift is the dominating process in the case of alkyl alkyne-tethered substrates. PMID:26550688

  16. C-N Coupling of Amides with Alcohols Catalyzed by N-Heterocyclic Carbene-Phosphine Iridium Complexes.

    PubMed

    Kerdphon, Sutthichat; Quan, Xu; Parihar, Vijay Singh; Andersson, Pher G

    2015-11-20

    N-Heterocyclic carbene-phosphine iridium complexes (NHC-Ir) were developed/found to be a highly reactive catalyst for N-monoalkylation of amides with alcohols via hydrogen transfer. The reaction produced the desired product in high isolated yields using a wide range of substrates with low catalyst loading and short reaction times. PMID:26489041

  17. Triply cyclometalated trinuclear iridium(iii) and trinuclear palladium(ii) complexes with a tri-mesoionic carbene ligand.

    PubMed

    Maity, Ramananda; Mekic, Amel; van der Meer, Margarethe; Verma, Amit; Sarkar, Biprajit

    2015-10-21

    The first example of a triply cyclometalated homopolynuclear tri-Ir(III) complex with additional carbene donors is presented. Cooperative catalysis and the interplay between homogenous and heterogeneous catalyses are discussed for the tri-Ir(III) complex and a related non-cyclometalated tri-Pd(II) complex. PMID:26264746

  18. Conformational Analysis of Olefin-Carbene Ruthenium Metathesis Diego Benitez, Ekaterina Tkatchouk, and William A. Goddard III*

    E-print Network

    Goddard III, William A.

    Conformational Analysis of Olefin-Carbene Ruthenium Metathesis Catalysts Diego Benitez, Ekaterina of acenaphthalene. Ruthenium-catalyzed olefin metathesis1 has become a power- ful tool for forming organic carbon-Fock exchange) functional, the relative ruthenium tricyclohexylphosphine (PCy3) bond dissociation energies

  19. Volume 202, number 1 FEBS 3737 June 1986 Laser-activated carbene labels the same residues in the

    E-print Network

    Junge, Wolfgang

    the structure of the proteolipids of Neurospora crassaand Escherichia coli ATP synthase by using a lipid in mitochondria and thylakoids. The reactive carbene was generated by a pulse from a frequency-doubled ruby laser to previous experiments [2]. 2. MATERIALS AND METHODS 2_1. Preparation iV. crassa was cultured and mito

  20. Synthesis of Naphthalenes through Three-Component Coupling of Alkynes, Fischer Carbene Complexes, and Benzaldehyde Hydrazones via Isoindole Intermediates

    PubMed Central

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K.; Herndon, James W.

    2008-01-01

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels–Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes. PMID:18351767

  1. Synthesis of naphthalenes through three-component coupling of alkynes, Fischer carbene complexes, and benzaldehyde hydrazones via isoindole intermediates.

    PubMed

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K; Herndon, James W

    2008-04-17

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels-Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes. PMID:18351767

  2. Theoretical tools to distinguish O-ylides from O-ylidic complexes in carbene-solvent interactions.

    PubMed

    Gómez, Sara; Restrepo, Albeiro; Hadad, C Z

    2015-11-25

    In this paper, we report the geometries and properties of 48 molecular species located on the MP2/6-311++G(d,p) PES of the fluorocarbene-(methanol)3 system. The structures were found by a combination of a stochastic search method, using a modified Metropolis acceptance test, and some hand constructed very symmetrical structures. We use several theoretical descriptors to categorize these species, focusing our attention on the interaction between the carbene carbon and the methanol oxygen, CcO, because this is the key interaction in the formation of O-ylides, ether products, and O-ylidic solvation complexes. These descriptors include natural charges and natural bond orbitals (NBO), CcO bond orders, CcO distances, energetic stabilities, and properties at bond critical points. Accordingly, the isomers were divided into four groups: ethers, fluorocarbene-methanol O-ylides, O-ylidic carbene-solvent complexes and hydrogen bonded carbene-solvent complexes. We found that the possibility of forming H-bonds among solvent molecules and between the carbene carbon and the hydrogen of the solvent molecule affects the stability, structure and nature of CcO interactions in O-ylides and O-ylidic complexes to the point of generating some diffuse borderlines between these two kinds of species. We determined which set of theoretical tools is suitable to better distinguish between them. Additionally, we clarify the nature of the relevant interactions in these species. PMID:26568481

  3. Asymmetric intramolecular ?-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic

    PubMed Central

    Luo, Chaosheng; Wang, Zhen; Huang, Yong

    2015-01-01

    Enantioselective ?-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular ?-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an ?-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using ?-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development. PMID:26644194

  4. First N-Heterocyclic Carbenes Relying on the Triazolone Structural Motif: Syntheses, Modifications and Reactivity.

    PubMed

    Jonek, Markus; Diekmann, Janina; Ganter, Christian

    2015-10-26

    4-Phenylsemicarbazide and 1,5-diphenylcarbazide are suitable starting materials for the syntheses of N-heterocyclic carbene (NHC) compounds with new backbone structures. In the first case, cyclisation and subsequent methylation leads to a cationic precursor whose deprotonation affords the triazolon-ylidene 2, which was converted to the corresponding sulfur and selenium adducts and a range of metal complexes. In contrast, cyclisation of diphenylcarbazide affords a neutral betain-type NHC-precursor 7, which is not in equilibrium with its carbene tautomer 7a. Precursor 7 can either be deprotonated to give the anionic NHC 8 or methylated at the N or O atom of the backbone resulting in two isomeric cationic species 16 and 20. Deprotonation of the latter two provides neutral NHC compounds with a carboxamide or carboximidate backbone, respectively. The ligand properties of the new NHC compounds were evaluated by IR and (77) Se NMR spectroscopy. Tolman electronic parameter (TEP) values range from 2050 to 2063?cm(-1) with the anionic NHC 8 being the best overall donor. PMID:26395132

  5. Surface Characterization and in situ Protein Adsorption Studies on Carbene-Modified Polymers.

    PubMed

    Nelson, Geoffrey W; Parker, Emily M; Singh, Kulveer; Blanford, Christopher F; Moloney, Mark G; Foord, John S

    2015-10-13

    Polystyrene thin films were functionalized using a facile two-step chemical protocol involving carbene insertion followed by azo-coupling, permitting the introduction of a range of chemical functional groups, including aniline, hexyl, amine, carboxyl, phenyl, phosphonate diester, and ethylene glycol. X-ray photoelectron spectroscopy (XPS) confirmed the success of the two-step chemical modification with a grafting density of at least 1/10th of the typical loading density (10(14)-10(15)) of a self-assembled monolayer (SAM). In situ, real-time quartz crystal microbalance with dissipation (QCM-D) studies show that the dynamics of binding of bovine serum albumin (BSA) are different at each modified surface. Mass, viscoelastic, and kinetic data were analyzed, and compared to cheminformatic descriptors (i.e., c log P, polar surface area) typically used for drug discovery. Results show that functionalities may either resist or adsorb BSA, and uniquely influence its adsorption dynamics. It is concluded that carbene-based surface modification can usefully influence BSA binding dynamics in a manner consistent with, and more robust than, traditional systems based on SAM chemistry. PMID:26391812

  6. N-Heterocyclic Carbene-Phosphinidene Complexes of the Coinage Metals.

    PubMed

    Doddi, Adinarayana; Bockfeld, Dirk; Nasr, Alexandre; Bannenberg, Thomas; Jones, Peter G; Tamm, Matthias

    2015-11-01

    Coinage metal complexes of the N-heterocyclic carbene-phosphinidene adduct IPr?PPh (IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by its reaction with CuCl, AgCl, and [(Me2 S)AuCl], which afforded the monometallic complexes [(IPr?PPh)MCl] (M=Cu, Ag, Au). The reaction with two equivalents of the metal halides gave bimetallic [(IPr?PPh)(MCl)2 ] (M=Cu, Au); the corresponding disilver complex could not be isolated. [(IPr?PPh)(CuOTf)2 ] was prepared by reaction with copper(I) trifluoromethanesulfonate. Treatment of [(IPr?PPh)(MCl)2 ] (M=Cu, Au) with Na(BAr(F) ) or AgSbF6 afforded the tetranuclear complexes [(IPr?PPh)2 M4 Cl2 ]X2 (X=BAr(F) or SbF6 ), which contain unusual eight-membered M4 Cl2 P2 rings with short cuprophilic or aurophilic contacts along the chlorine-bridged M???M axes. Complete chloride abstraction from [(IPr?PPh)(AuCl)2 ] was achieved with two equivalents of AgSbF6 in the presence of tetrahydrothiophene (THT) to form [(IPr?PPh){Au(THT)}2 ][SbF6 ]2 . The cationic tetra- and dinuclear complexes were used as catalysts for enyne cyclization and carbene transfer reactions. PMID:26365325

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

    PubMed

    Dahcheh, Fatme; Stephan, Douglas W

    2015-01-28

    A series of bis-carbene Ru-hydride species, including (IMes)(Im(OMe)2)(PPh3)RuHCl (1) and (SIMes)(Me2Im(OMe)2)(PPh3)RuHCl (2) were prepared and subsequently shown to react with aryl-vinyl-sulfides to give the bis-carbene-alkylidene complexes: Im(OMe)2(SIMes)RuCl(SR)(=CHCH3) (R = p-FC6H4 (3), p-(NO2)C6H4 (4)), Im(OMe)2(IMes)RuCl(=CHCH3)(SPh) (5), Me2Im(OMe)2(SIMes)RuCl(=CHCH3)(SPh) (6), Im(OMe)2(SIMes)(F5C6S)RuCl(=CHR) (R = C4H9 (9), C5H11 (10)). The activity of these species in the standard Grubbs' tests for ring-opening metathesis polymerization, ring-closing and cross-metathesis are reported. Although these thiolate derivatives are shown to exhibit modest metathesis activities, the reactivity is enhanced in the presence of BCl3. PMID:25462569

  8. Stretch Out or Fold Back? Conformations of Dinuclear Gold(I) N-Heterocyclic Carbene Macrocycles.

    PubMed

    Kobialka, Stefanie; Müller-Tautges, Christina; Schmidt, Melanie T S; Schnakenburg, Gregor; Hollóczki, Oldamur; Kirchner, Barbara; Engeser, Marianne

    2015-07-01

    We report the synthesis and characterization of 12 new dinuclear gold(I) N-heterocyclic carbene (NHC) complexes and the corresponding imidazolium precursors. The focus lies in a systematic study of conformational changes and intra- and intermolecular gold-gold and ?-? interactions of dinuclear gold(I) carbene complexes. Common to all members of the series of gold macrocycles are NHC ligands on the basis of imidazole with ethyl side chains and bromide as well as hexafluorophosphate counterions, respectively. The compounds vary in the length of a flexible alkyl linker between the NHC units. For the methylene and ethylene bridged macrocycles, a ring inversion movement can be observed by VT-NMR. In total, 11 molecular structures have been characterized by X-ray diffraction. Open ring conformations with intermolecular ?-? and Au-Au interactions prevail, but a backfolded conformation with a short intramolecular Au-Au distance has been found for the ethylene-bridged species. The presence of Au-Au interactions could be proven by quantum chemical calculations. PMID:26087332

  9. Toward New Organometallic Architectures: Synthesis of Carbene-Centered Rhodium and Palladium Bisphosphine Complexes. Stability and Reactivity of [PC(BIm)PRh(L)][PF6] Pincers.

    PubMed

    Plikhta, Andriy; Pöthig, Alexander; Herdtweck, Eberhardt; Rieger, Bernhard

    2015-10-01

    In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PC(BIm)P pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl2 and [?-OCH3Rh(COD)]2 smoothly forming the target organometallics [PC(BIm)PPdCl][PF6] and [PC(BIm)PRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PC(BIm)PRh(L)][PF6] reveals significant thermal stability of the PC(BIm)PRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PC(BIm)PRh(I) complex is a sufficiently stable compound, with the potential to be applied in catalysis. PMID:26390389

  10. Stable compactifications

    SciTech Connect

    Accetta, F.S.; Gleiser, M.; Holman, R.; Kolb, E.W.

    1986-03-01

    We show that compactifications of theories with extra dimensions are unstable if due to monopole configurations of an antisymmetric tensor field balanced against one-loop Casimir corrections. In the case of ten dimensional supergravity, it is possible, at least for a portion of the phase space, to achieve a stable compactification without fine-tuning by including the contribution of fermionic condensates to the monopole configurations. 23 refs., 2 figs.

  11. Exploiting Acyl and Enol Azolium Intermediates via NHeterocyclic Carbene Catalyzed Reactions of Alpha-Reducible Aldehydes

    PubMed Central

    Vora, Harit U.; Wheeler, Philip

    2013-01-01

    N-heterocyclic carbenes are well known for their role in catalyzing benzoin and Stetter reactions: the generation of acyl anion equivalents from simple aldehydes to react with a variety of electrophiles. However, when an aldehyde bearing a leaving group or unsaturation adjacent to the acyl anion equivalent is subjected to an NHC, a new avenue of reactivity is unlocked, leading to a number of novel transformations which can generate highly complex products from simple starting materials, many of which are assembled through unconventional bond disconnections. The field of these new reactions - those utilizing ?-reducible aldehydes to access previously unexplored catalytic intermediates – has expanded rapidly in the past eight years. This review aims to provide the reader with a historical perspective on the underlying discoveries that led to the current state of the art, a mechanistic description of these reactions, and a summary of the recent advances in this area. PMID:23538785

  12. Tuning the electronic and ligand properties of remote carbenes: a theoretical study.

    PubMed

    Borthakur, Bitupon; Rahman, Taskia; Phukan, Ashwini K

    2014-11-21

    The effect of annulation and carbonylation on the electronic and ligating properties of remote N-heterocyclic carbenes (rNHCs) has been studied quantum-chemically. The thermodynamic stability of these complexes has been assessed on the basis of their hydrogenation and stabilization energies, while HOMO-LUMO gaps are used to measure the kinetic stabilities. Annulated/carbonylated rNHCs are found to be weaker ? donors but better ? acceptors compared with the parent rNHCs. The reactivity of these rNHCs has been studied by evaluating their nucleophilicity and electrophilicity indices. The nucleophilicity values are in good agreement with the ? basicities of all of the rNHCs. The (31)P NMR chemical shifts of the corresponding rNHC-phosphinidene adducts have been calculated and found to correlate well with the ? acidities of these rNHCs. PMID:25340967

  13. Cooperative Catalysis by Carbenes and Lewis Acids in a Highly Stereoselective Route to ?-Lactams

    PubMed Central

    Raup, Dustin E. A.; Cardinal-David, Benoit; Holte, Dane; Scheidt, Karl A.

    2010-01-01

    Enzymes are a continuing source of inspiration for the design of new chemical reactions that proceed with efficiency, high selectivity and minimal waste. In many biochemical processes, different catalytic species, such as Lewis acids and bases, are involved in precisely orchestrated interactions to activate reactants simultaneously or sequentially. Employing this type of cooperative catalysis, in which two or more catalytic cycles operate concurrently to achieve one overall transformation, has great potential to enhance known reactivity and drive the development of new chemical reactions with high value. In this disclosure, a cooperative N-heterocyclic carbene/Lewis acid catalytic system promotes the addition of homoenolate equivalents to hydrazones generating highly substituted ?-lactams in moderate to good yields and high levels of diastereo- and enantioselectivity. PMID:20729898

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

    PubMed Central

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

    2008-01-01

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

  15. Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis.

    PubMed

    Marx, Vanessa M; Sullivan, Alexandra H; Melaimi, Mohand; Virgil, Scott C; Keitz, Benjamin K; Weinberger, David S; Bertrand, Guy; Grubbs, Robert H

    2015-02-01

    An expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3?ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340,000, at a catalyst loading of only 1?ppm. This is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable to the industrial-scale production of linear ?-olefins (LAOs) and other terminal-olefin products. PMID:25522160

  16. Ruthenium indenylidene complexes bearing N-alkyl/N-mesityl-substituted N-heterocyclic carbene ligands.

    PubMed

    Yu, Baoyi; Hamad, Fatma B; Sels, Bert; Van Hecke, Kristof; Verpoort, Francis

    2015-07-14

    We report on the synthesis and characterization of second generation ruthenium indenylidene catalysts bearing unsymmetrical N-heterocyclic carbene (NHC) ligands denoted as RuCl2(3-phenyl-1-indenylidene)(1-mesityl-3-R-4,5-dihydroimidazol-2-ylidene)(PCy3), in which R is methyl 8a, octyl 8b or cyclohexyl 8c. The characterization of 8a-c was performed by NMR spectroscopy, elemental analysis, IR, HRMS and single-crystal X-ray diffraction analysis. In addition, the catalytic activity of the obtained initiators was evaluated in various representative metathesis reactions. The results reveal that the complexes 8a-c, bearing an N-alkyl side on the NHC, show a faster catalytic initiation than the reference complex 2. Complex 8a, which performs the best among the investigated indenylidene complexes, exhibits slower initiation but better overall efficiency than its benzylidene analogue 1c, especially in a low catalyst loading. PMID:26052999

  17. A search for thermal isomerization of olefins to carbenes: Thermal generations of the silicon-nitrogen double bond

    SciTech Connect

    Zhang, Xianping.

    1990-09-21

    The first part of this thesis will search for the thermal isomerization of olefins to carbenes which is predicted to be a high energy process by calculations and has only been observed in a few strained olefins. The possibility of thermal isomerization of simple olefins to carbenes will be explored. Substitution of a silyl group on the double bond of an olefin allows a potential intermediate which has a {beta}-radical to the silyl group during the cis-trans isomerization. The effects of a trimethylsilyl group on this isomerization are the subject of this study. The second part of this thesis will include the generation and chemistry of intermediates containing a silicon-nitrogen double bond. The isomerization of parent silanimine to the aminosilylene was calculated to be a high energy process. New approaches to the silicon-nitrogen double bond will also be presented. 92 refs., 12 figs., 11 tabs.

  18. Expedient Mechanosynthesis of N,N-Dialkyl Imidazoliums and Silver(I)-Carbene Complexes in a Ball-Mill.

    PubMed

    Beillard, Audrey; Golliard, Ethan; Gillet, Valentin; Bantreil, Xavier; Métro, Thomas-Xavier; Martinez, Jean; Lamaty, Frédéric

    2015-12-01

    The absence of solvent, associated with intensive mechanical agitation, allowed the first mechanosynthesis of high-value silver(I)-carbene complexes and the corresponding N,N-dialkylimidazolium precursors. This procedure gave outstanding results in terms of yield and reaction time, when compared to solution-based conditions previously described in literature, and was generalized to unprecedented compounds. Silver(I)-carbene complexes could either be obtained from N,N-dialkylimidazolium salts or directly from imidazole and alkyl halides in a one-pot two-step procedure without isolating the imidazolium intermediate. Additionally, an efficient one-pot three-step sequence, including imidazole alkylation, silver metalation, and transmetalation is reported. PMID:26489706

  19. Efficient synthesis strategies by application of transition metal-catalyzed carbene/nitrene insertions into C-H bonds.

    PubMed

    Egger, Julian; Carreira, Erick M

    2014-04-01

    Transition metal-catalyzed insertion of carbenes and nitrenes into C-H bonds has become a powerful tool for the construction of C-C and C-N bonds in the synthesis of complex natural products. In this Highlight, a selection of syntheses are detailed involving the implementation of C-H insertion reactions leading to strategies marked by improved efficiency. PMID:24589531

  20. Energy Transfer in a Hybrid Ir(III) Carbene-Pt(II) Acetylide Assembly for Efficient Hydrogen Production.

    PubMed

    Yu, Zhen-Tao; Yuan, Yong-Jun; Chen, Xin; Cai, Jian-Guang; Zou, Zhi-Gang

    2015-07-01

    A new heterometallic supramolecular complex, consisting of an iridium carbene-based unit appended to a platinum terpyridine acetylide unit, representing a new Ir(III) -Pt(II) structural motif, was designed and developed to act as an active species for photocatalytic hydrogen production. The results also suggested that a light-harvesting process is essential to realize the solar-to-fuel conversion in an artificial system as illustrated in the natural photosynthetic system. PMID:26096270

  1. The Pd-catalyzed synthesis of benzofused carbo- and heterocycles through carbene migratory insertion/carbopalladation cascades with tosylhydrazones.

    PubMed

    Paraja, Miguel; Carmen Pérez-Aguilar, M; Valdés, Carlos

    2015-10-29

    The Pd-catalyzed reaction between o-iodoallylbenzene and tosylhydrazones gives rise to indene derivatives through a process that involves a carbene migratory insertion followed by an intramolecular carbopalladation, with the formation of two C-C bonds on the same carbon atom. The same strategy has also been applied for the synthesis of 2,3-disubstituted benzofurans and indenones by selecting the appropriate o-substituted iodoarene. PMID:26400071

  2. Enantioselective sulfonation of enones with sulfonyl imines by cooperative N-heterocyclic-carbene/thiourea/tertiary-amine multicatalysis.

    PubMed

    Jin, Zhichao; Xu, Jianfeng; Yang, Song; Song, Bao-An; Chi, Yonggui Robin

    2013-11-18

    Many hands make light work: In an organocatalytic asymmetric sulfonation of enones, the activation of a sulfonyl imine by an N-heterocyclic carbene (NHC) catalyst led to the release of a sulfinic anion, which underwent nucleophilic addition to the enone. The enantioselectivity of the process was controlled by a chiral thiourea/amine co-catalyst through anion recognition and hydrogen-bonding interactions. Tol=p-tolyl. PMID:24115649

  3. Multicomponent synthesis of chiral bidentate unsymmetrical unsaturated N-heterocyclic carbenes: copper-catalyzed asymmetric C-C bond formation.

    PubMed

    Jahier-Diallo, Claire; Morin, Marie S T; Queval, Pierre; Rouen, Mathieu; Artur, Isabelle; Querard, Pierre; Toupet, Loic; Crévisy, Christophe; Baslé, Olivier; Mauduit, Marc

    2015-01-12

    A multicomponent strategy was applied to the synthesis of chiral bidentate unsaturated hydroxyalkyl- and carboxyalkyl-N-heterocyclic carbene (NHC) precursors. The newly developed low-cost chiral ligands derived from amino alcohols and amino acids were evaluated in copper-catalyzed asymmetric conjugated addition and asymmetric allylic alkylation, which afforded the desired tertiary and quaternary carbon stereocenters with excellent regio- and enantioselectivities (up to 99:1 e.r.). PMID:25421857

  4. Preparation of a N-Heterocyclic Carbene Nickel(II) Complex: Synthetic Experiments in Current Organic and Organometallic Chemistry

    ERIC Educational Resources Information Center

    Ritleng, Vincent; Brenner, Eric; Chetcuti, Michael J.

    2008-01-01

    A four-part experiment that leads to the synthesis of a cyclopentadienyl chloro-nickel(II) complex bearing a N-heterocyclic carbene (NHC) ligand is presented. In the first part, the preparation of 1,3-bis-(2,4,6-trimethylphenyl)imidazolium chloride (IMes[middle dot]HCl) in a one-pot procedure by reaction of 2,4,6-trimethylaniline with…

  5. "Hummingbird" behaviour of N-heterocyclic carbenes stabilises out-of-plane bonding of AuCl and CuCl units.

    PubMed

    Teci, Matthieu; Brenner, Eric; Matt, Dominique; Gourlaouen, Christophe; Toupet, Loic

    2015-07-27

    An N-heterocyclic carbene substituted by two expanded 9-ethyl-9-fluorenyl groups was shown to bind an AuCl unit in an unusual manner, namely with the Au?X rod sitting out of the plane defined by the heterocyclic carbene unit. As shown by X-ray studies and DFT calculations, the observed large pitch angle (21°) arises from an easy displacement of the gold(I) atom away from the carbene lone-pair axis, combined with the stabilisation provided by weak CH???Au interactions involving aliphatic and aromatic H atoms of the NHC wingtips. Weak, intermolecular Cl???H bonds are likely to cooperate with the H???Au interactions to stabilise the out-of-plane conformation. A general belief until now was that tilt angles in NHC complexes arise mainly from steric effects within the first coordination sphere. PMID:26130507

  6. Nanofiber composites containing N-heterocyclic carbene complexes with antimicrobial activity

    PubMed Central

    Elzatahry, Ahmed A; Al-Enizi, Abdullah M; Elsayed, Elsayed Ahmed; Butorac, Rachel R; Al-Deyab, Salem S; Wadaan, Mohammad AM; Cowley, Alan H

    2012-01-01

    This report concerns nanofiber composites that incorporate N-heterocyclic carbenes and the use of such composites for testing antimicrobial and antifungal activities. The nanofiber composites were produced by electrospinning mixtures of the gold chloride or gold acetate complexes of a bis(imino)acenaphthene (BIAN)-supported NHC with aqueous solutions of polyvinyl alcohol (PVA). The products were characterized by scanning-electron microscopy, which revealed that nanofibers in the range of 250–300 nm had been produced. The biological activities of the nanofiber composites were tested against two Gram-positive bacteria, six Gram-negative bacteria, and two fungal strains. No activity was evident against the fungal strains. However, the gold chloride complex was found to be active against all the Gram-positive pathogens and one of the Gram-negative pathogens. It was also found that the activity of the produced nanofibers was localized and that no release of the bioactive compound from the nanofibers was evident. The demonstrated antimicrobial activities of these novel nanofiber composites render them potentially useful as wound dressings. PMID:22745545

  7. A highly conjugated benzimidazole carbene-based ruthenium sensitizer for dye-sensitized solar cells.

    PubMed

    Ho, Shih-Yu; Su, Chaochin; Li, Chung-Yen; Prabakaran, Kumaresan; Shen, Ming-Tai; Chen, Ying-Fan; Chang, Wei-Chun; Tingare, Yogesh S; Akula, Suribabu; Tsai, Sheng-Han; Li, Wen-Ren

    2013-09-01

    A new type of carbene-based ruthenium sensitizer, CB104, with a highly conjugated ancillary ligand, diphenylvinylthiophene-substituted benzimidazolepyridine, was designed and developed for dye-sensitized solar cell applications. The influence of the thiophene antenna on the performance of the cell anchored with CB104 was investigated. Compared with the dye CBTR, the conjugated thiophene in the ancillary ligand of CB104 enhanced the molar extinction coefficient of the intraligand ?-?* transition and the intensity of the lower energy metal-to-ligand charge-transfer band. However, the incident photon-to-current conversion efficiency spectrum of the cell anchored with CB104 (0.15?mM) showed a maximum of 63?% at 420?nm. The cell sensitized with the dye CB104 attained a power conversion efficiency of 7.30?%, which was lower than that of the cell with nonconjugated sensitizer CBTR (8.92?%) under the same fabrication conditions. The variation in the performance of these two dyes demonstrated that elongating the conjugated light-harvesting antenna resulted in the reduction of short-circuit photocurrent density, which might have been due to the aggregation of dye molecules. In the presence of a coabsorbate, chenodeoxycholic acid, the CB104-sensitized cell exhibited an enhanced photocurrent density and achieved a photovoltaic efficiency of 8.36?%. PMID:23832840

  8. Biological Screening of Newly Synthesized BIAN N-Heterocyclic Gold Carbene Complexes in Zebrafish Embryos

    PubMed Central

    Farooq, Muhammad; Abu Taha, Nael; Butorac, Rachel R.; Evans, Daniel Anthony; Elzatahry, Ahmed A.; Elsayed, Elsayed Ahmed; Wadaan, Mohammad A. M.; Al-Deyab, Salem S.; Cowley, Alan H.

    2015-01-01

    N-Heterocyclic carbene (NHC) metal complexes possess diverse biological activities but have yet to be extensively explored as potential chemotherapeutic agents. We have previously reported the synthesis of a new class of NHC metal complexes N-heterocyclic with acetate [IPr(BIAN)AuOAc] and chloride [IPr(BIAN)AuCl] ligands. In the experiments reported herein, the zebrafish embryos were exposed to serial dilutions of each of these complexes for 10–12 h. One hundred percent mortality was observed at concentrations ?50 µM. At sub-lethal concentrations (10–30 µM), both compounds influenced zebrafish embryonic development. However, quite diverse categories of abnormalities were found in exposed embryos with each compound. Severe brain deformation and notochord degeneration were evident in the case of [IPr(BIAN)AuOAc]. The zebrafish embryos treated with [IPr(BIAN)AuCl] exhibited stunted growth and consequently had smaller body sizes. A depletion of 30%–40% glutathione was detected in the treated embryos, which could account for one of the possible mechanism of neurotoxicity. The fact that these compounds are capable of both affecting the growth and also compromising antioxidant systems by elevating intracellular ROS production implies that they could play an important role as a new breed of therapeutic molecules. PMID:26501273

  9. Correlations and Contrasts in Homo- and Heteroleptic Cyclic (Alkyl)(amino)carbene-Containing Pt(0) Complexes.

    PubMed

    Arnold, Nicole; Braunschweig, Holger; Brenner, Peter B; Celik, Mehmet Ali; Dewhurst, Rian D; Haehnel, Martin; Kramer, Thomas; Krummenacher, Ivo; Marder, Todd B

    2015-08-24

    An improved synthetic route to homoleptic complex [Pt(CAAC(Me))2] (CAAC = cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAAC(Me))(PR3)] are presented. Although the homoleptic complex was found to be inert to many reagents, oxidative addition and metal-only Lewis pair (MOLP) formation was observed from one of the heteroleptic complexes. The spectroscopic, structural, and electrochemical properties of the zero-valent complexes were explored in concert with density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The homoleptic [Pt(CAAC)2] and heteroleptic [Pt(CAAC)(PR3)] complexes were found to be similar in their spectroscopic and structural properties, but their electrochemical behavior and reactivity differ greatly. The unusually strong color of the CAAC-containing Pt(0) complexes was investigated by TD-DFT calculations and attributed to excitations into the LUMOs of the complexes, which are predominantly composed of bonding ? interactions between Pt and the CAAC carbon atoms. PMID:26241579

  10. Conformation analysis of triphenylphosphine in trans and cis triphenylphosphine-substituted Fischer carbene complexes

    NASA Astrophysics Data System (ADS)

    Landman, Marilé; Levell, Tamzyn; van Rooyen, Petrus H.; Conradie, Jeanet

    2014-05-01

    The synthesis and selected crystal structures of novel (M = Cr or Mo) and known (M = W) [(CO)4(PPh3)M = C(OEt)R] complexes, M = Cr, R = 2-thienyl (1), 2-furyl (2); M = Mo, R = 2-thienyl (3), 2-furyl (4); M = W, R = 2-thienyl (5), 2-furyl (6), are presented. Experimental crystal structures and DFT calculations of selected trans- and cis-triphenylphosphine-substituted Fischer carbene complexes, illustrate that the minimum energy conformation of triphenylphosphine (PPh3) in octahedral [(CO)4(PPh3)ML]-complexes generally have distinct features that can be described in terms of the "plane of nadir energy", a plane linking all points of minimum steric compression between the ligands. The generally observed orientation of PPh3 involves a correlated feathering of the phenyl groups with the PCipso bond of one phenyl group orientated near parallel to the nadir plane, and a meta carbon (Cm) of the other two phenyl groups orientated as near as possible to the nadir plane, orthogonal to the first. Although the orientation of PPh3 in 6-trans, [(CO)4(PPh3)W = C(OEt)2-furyl], deviates from this, DFT correctly calculated the unexpected and not generally observed PPh3 orientation.

  11. 4-Alkylated Silver–N-Heterocyclic Carbene (NHC) Complexes with Cytotoxic Effects in Leukemia Cells

    PubMed Central

    Sandtorv, Alexander H; Leitch, Calum; Bedringaas, Siv Lise; Gjertsen, Bjørn Tore; Bjørsvik, Hans-René

    2015-01-01

    Computational chemistry has shown that backbone-alkylated imidazoles ought to be efficient ligands for transition metal catalysts with improved carbene-to-metal donation. In this work, such alkylated imidazoles were synthesized and complexed with silver(I) by means of an eight/nine-step synthetic pathway we devised to access a new class of biologically active silver complexes. The synthesis involves selective iodination of the imidazole backbone, followed by Sonogashira coupling to replace the backbone iodine. The installed alkyne moiety is then subjected to reductive hydrogenation with Pearlman’s catalyst. The imidazole N1 atom is arylated by the palladium-catalyzed Buchwald N-arylation method. The imidazole N3 position was then methylated with methyl iodine, whereupon the synthesis was terminated by complexation of the imidazolium salt with silver(I) oxide. The synthetic pathway provided an overall yield of ?20?%. The resulting complexes were tested in vitro against HL60 and MOLM-13 leukemic cells, two human-derived cell lines that model acute myeloid leukemia. The most active compounds exhibiting low IC50 values of 14 and 27??M, against HL60 and MOLM-13 cells, respectively. The imidazole side chain was found to be essential for high cytotoxicity, as the imidazole complex bearing a C7 side chain at the 4-position was four- to sixfold more potent than the corresponding imidazole elaborated with a methyl group. PMID:26250720

  12. Effects of Phosphine-Carbene Substitutions on the Electrochemical and Thermodynamic Properties of Nickel Complexes

    SciTech Connect

    Galan, Brandon R.; Wiedner, Eric S.; Helm, Monte L.; Linehan, John C.; Appel, Aaron M.

    2014-05-12

    Nickel(II) complexes containing chelating N-heterocyclic carbene-phosphine ligands ([NiL2](BPh4)2, for which L = [MeIm(CH2)2PR2]) have been synthesized for the purpose of studying how this class of ligand effects the electrochemical properties compared to the nickel bis- diphosphine analogues. The nickel complexes were synthesized and characterized by x-ray crystallography and electrochemical methods. Based on the half wave potentials (E1/2), substitution of an NHC for one of the phosphines in a diphoshine ligand results in shifts in potential to 0.6 V to 1.2 V more negative than the corresponding nickel bis-diphosphine complexes. These quantitative results highlight the substantial effect that NHC ligands can have upon the electronic properties of the metal complexes. BRG, JCL, and AMA acknowledge the support by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MLH acknoledges the support of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  13. Stereoelectronic effects in C-H bond oxidation reactions of Ni(I) N-heterocyclic carbene complexes.

    PubMed

    Poulten, Rebecca C; López, Isidoro; Llobet, Antoni; Mahon, Mary F; Whittlesey, Michael K

    2014-07-21

    Activation of O2 by the three-coordinate Ni(I) ring-expanded N-heterocyclic carbene complexes Ni(RE-NHC)(PPh3)Br (RE-NHC = 6-Mes, 1; 7-Mes, 2) produced the structurally characterized dimeric Ni(II) complexes Ni(6-Mes)(Br)(?-OH)(?-O-6-Mes')NiBr (3) and Ni(7-Mes)(Br)(?-OH)(?-O-7-Mes')NiBr (4) containing oxidized ortho-mesityl groups from one of the carbene ligands. NMR and mass spectrometry provided evidence for further oxidation in solution to afford bis-?-aryloxy compounds; the 6-Mes derivative was isolated, and its structure was verified. Low-temperature UV-visible spectroscopy showed that the reaction between 1 and O2 was too fast even at ca. -80 °C to yield any observable intermediates and also supported the formation of more than one oxidation product. Addition of O2 to Ni(I) precursors containing a less electron-donating diamidocarbene (6-MesDAC, 7) or less bulky 6- or 7-membered ring diaminocarbene ligands (6- or 7-o-Tol; 8 and 9) proceeded quite differently, affording phosphine and carbene oxidation products (Ni(O?PPh3)2Br2 and (6-MesDAC)?O) and the mononuclear Ni(II) dibromide complexes (Ni(6-o-Tol)(PPh3)Br2 (10) and (Ni(7-o-Tol)(PPh3)Br2 (11)) respectively. Electrochemical measurements on the five Ni(I) precursors show significantly higher redox potentials for 1 and 2, the complexes that undergo oxygen atom transfer from O2. PMID:24972307

  14. Nucleophilic addition of amines to ruthenium carbenes: ortho-(alkynyloxy)benzylamine cyclizations towards 1,3-benzoxazines.

    PubMed

    González-Rodríguez, Carlos; Suárez, José Ramón; Varela, Jesús A; Saá, Carlos

    2015-02-23

    A new ruthenium-catalyzed cyclization of ortho-(alkynyloxy)benzylamines to dihydro-1,3-benzoxazines is reported. The cyclization is thought to take place via the vinyl ruthenium carbene intermediates which are easily formed from [Cp*RuCl(cod)] and N2 CHSiMe3 . The mild reaction conditions and the efficiency of the procedure allow the easy preparation of a broad range of new 2-vinyl-2-substituted 1,3-benzoxazine derivatives. Rearrangement of an internal C(sp) in the starting material into a tetrasubstituted C(sp(3) ) atom in the final 1,3-benzoxazine is highly remarkable. PMID:25640908

  15. Extending N-Heterocyclic Carbene Ligands into the Third Dimension: A New Type of Hybrid Phosphazane/NHC System

    E-print Network

    Roth, Torsten; Vasilenko, Vladislav; Benson, Callum G. M.; Wadepohl, Hubert; Wright, Dominic S.; Gade, Lutz H.

    2015-02-13

    that the cyclophosphazane carbene is a powerful electron donor ligand. The strong s-donor character of 3 is consistent with the presence of the donor-P atoms adjacent to the NCN-unit. One of the most notable features of the solid-state structures of the iridium complexes 4... . Even a?er the addition of an excess of the iridium precursor no further species were detected by 31P NMR, indicating that the lone pair of the second phosphorus atom is not accessible for coordination. The solid-Chem. Sci., 2015, 6, 2506–2510 | 2507...

  16. Evidencing an inner-sphere mechanism for NHC-Au(I)-catalyzed carbene-transfer reactions from ethyl diazoacetate

    PubMed Central

    Fructos, Manuel R; Urbano, Juan

    2015-01-01

    Summary Kinetic experiments based on the measurement of nitrogen evolution in the reaction of ethyl diazoacetate (N2CHCO2Et, EDA) and styrene or methanol catalyzed by the [IPrAu]+ core (IPr = 1,3-bis(diisopropylphenyl)imidazole-2-ylidene) have provided evidence that the transfer of the carbene group CHCO2Et to the substrate (styrene or methanol) takes place in the coordination sphere of Au(I) by means of an inner-sphere mechanism, in contrast to the generally accepted proposal of outer-sphere mechanisms for Au(I)-catalyzed reactions. PMID:26664649

  17. Novel dimetal bridging carbene complexes derived from a terminal carbonyl dimetal compound. Syntheses, structures and reactivities of 7H-indene-coordinated diiron bridging carbene complexes.

    PubMed

    Zhang, Lei; Sun, Jie; Zhu, Huping; Xu, Qiang; Tsumori, Nobuko; Chen, Jiabi

    2006-09-28

    Pentacarbonyl-7H-indenediiron, [Fe2(CO)5(eta3,eta5-C9H8)] (1), reacts with aryllithium, ArLi (Ar = C6H5, p-C6H5C6H4), followed by alkylation with Et3OBF4 to give novel 7H-indene-coordinated diiron bridging alkoxycarbene complexes [Fe2{mu-C(OC2H5)Ar}(CO)4(eta4,eta4-C9H8)] (2, Ar = C6H5; 3, Ar = p-C6H5C6H4). Complexes 2 and 3 react with HBF4.Et2O at low temperature to yield cationic bridging carbyne complexes [Fe2(mu-CAr)(CO)4(eta4,eta4-C9H8)]BF4 (4, Ar = C6H5; 5, Ar = p-C6H5C6H4). Cationic 4 and 5 react with NaBH4 in THF at low temperature to afford diiron bridging arylcarbene complexes [Fe2{mu-C(H)Ar}(CO)4(eta4,eta4-C9H8)] (6, Ar = C6H5; 7, Ar = p-C6H5C6H4). The similar reactions of 4 and 5 with NaSC6H4CH3-p produce the bridging arylthiocarbene complexes [Fe2{mu-C(Ar)SC6H4CH3-p}(CO)4(eta4,eta4-C9H8)] (8, Ar = C6H5; 9, Ar = p-C6H5C6H4). Cationic 4 and 5 can also react with anionic carbonylmetal compounds Na[M(CO)5(CN)] (M = Cr, Mo, W) to give the diiron bridging aryl(pentacarbonylcyanometal)carbene complexes [Fe2{mu-C(Ar)NCM(CO)5}(CO)4(eta4,eta4-C9H8)] (10, Ar = C6H5, M = Cr; 11, Ar = p-C6H5C6H4, M = Cr; 12, Ar = C6H5, M = Mo; 13, Ar = p-C6H5C6H4, M = Mo; 14, Ar = C6H5, M = W; 15, Ar = p-C6H5C6H4, M = W). Interestingly, in CH2Cl2 solution at room temperature complexes 10-15 were transformed into the isomerized 7H-indene-coordinated monoiron complexes [Fe(CO)2(eta5-C9H8)C(Ar)NCM(CO)5] (16, Ar = C6H5, M = Cr; 17, Ar = p-C6H5C6H4, M = Cr; 18, Ar = C6H5, M = Mo; 19, Ar = p-C6H5C6H4, M = Mo; 20, Ar = C6H5, M = W; 21, Ar = p-C6H5C6H4, M = W), while complex 3 was converted into a novel ring addition product [Fe2{C(OC2H5)C6H4C6H5-p-(eta2,eta5-C9H8)}(CO)5] (22) under the same conditions. The structures of complexes 2, 6, 8, 14, 18 and 22 have been established by X-ray diffraction studies. PMID:16967119

  18. Synthesis of 4-alkynylquinazolines: Pd-Cu-cocatalyzed coupling of quinazoline-4-tosylates with terminal alkynes using N-heterocyclic carbenes as ligands.

    PubMed

    Peng, Yiyuan; Huang, Ping; Wang, Yu; Zhou, Yirong; Yuan, Jianjun; Yang, Qin; Jiang, Xin; Deng, Zhihong; Xu, Jingshi

    2014-08-21

    A Pd-Cu-cocatalyzed coupling reaction of quinazoline-4-tosylates with terminal alkynes using N-heterocyclic carbenes (NHC) as ligands is described, providing 4-alkynylquinazolines in good to excellent yields. This transformation proceeds under mild conditions with high efficiency, which is attractive for focused compound library construction. PMID:24986122

  19. "N"-Heterocyclic Carbene-Catalyzed Reaction of Chalcone and Cinnamaldehyde to Give 1,3,4-Triphenylcyclopentene Using Organocatalysis to Form a Homoenolate Equivalent

    ERIC Educational Resources Information Center

    Snider, Barry B.

    2015-01-01

    In this experiment, students carry out a modern organocatalytic reaction using IMes·HCl and NaOH to catalyze the formation of 1,3,4-triphenylcyclopentene from cinnamaldehyde and chalcone in water. Deprotonation of IMes·HCl with NaOH forms the "N"-heterocyclic carbene IMes that reacts with cinnamaldehyde to form a homoenolate equivalent…

  20. Synthesis of Pd-N-heterocyclic carbene Pd-catalyst and its application in MW-assisted Heck and Suzuki reaction

    EPA Science Inventory

    The first Pd-N-heterocyclic carbene (NHC) complex in the form of organic silica is prepared using sol-gel method and its application in Heck and Suzuki reactions are demonstrated. These C-C coupling reactions proceeded efficiently under the influence of microwave irradiation, wit...

  1. Iridium(I) complexes with anionic N-heterocyclic carbene ligands as catalysts for the hydrogenation of alkenes in nonpolar media.

    PubMed

    Kolychev, Eugene L; Kronig, Sabrina; Brandhorst, Kai; Freytag, Matthias; Jones, Peter G; Tamm, Matthias

    2013-08-21

    A series of lithium complexes of anionic N-heterocyclic carbenes that contain a weakly coordinating borate moiety (WCA-NHC) was prepared in one step from free N-heterocyclic carbenes by deprotonation with n-butyl lithium followed by borane addition. The reaction of the resulting lithium-carbene adducts with [M(COD)Cl]2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) afforded zwitterionic rhodium(I) and iridium(I) complexes of the type [(WCA-NHC)M(COD)], in which the metal atoms exhibit an intramolecular interaction with the N-aryl groups of the carbene ligands. For M = Rh, the neutral complex [(WCA-NHC)Rh(CO)2] and the ate complex (NEt4)[(WCA-NHC)Rh(CO)2Cl] were prepared, with the latter allowing an assessment of the donor ability of the ligand by IR spectroscopy. The zwitterionic iridium-COD complexes were tested as catalysts for the homogeneous hydrogenation of alkenes, which can be performed in the presence of nonpolar solvents or in the neat alkene substrate. Thereby, the most active complex showed excellent stability and activity in hydrogenation of alkenes at low catalyst loadings (down to 10 ppm). PMID:23883399

  2. N-Heterocyclic carbene ligands bearing poly(ethylene glycol) chains: effect of the chain length on palladium-catalyzed coupling reactions employing aryl chlorides.

    PubMed

    Fujihara, Tetsuaki; Yoshikawa, Takahiro; Satou, Motoi; Ohta, Hidetoshi; Terao, Jun; Tsuji, Yasushi

    2015-12-21

    N-Heterocyclic carbenes bearing poly(ethylene glycol) chains of different lengths have been designed and employed as ligands in palladium-catalyzed coupling reactions. The catalyst system having longer chains was found to be highly efficient for Suzuki-Miyaura coupling and borylation reactions employing aryl chlorides under mild reaction conditions. PMID:26465096

  3. Domino Michael addition-carbene rearrangement-cyclization reaction of 1-alkynyl(aryl)-lambda3-bromanes with 2-mercapto-1,3-benzazoles.

    PubMed

    Ochiai, Masahito; Tada, Norihiro

    2005-10-28

    Exposure of 1-alkynyl[p-(trifluoromethyl)phenyl](tetrafluoroborato)-lambda3-bromanes to 2-mercaptobenzimidazole or benzothiazole in dichloromethane at 0 degrees C under argon resulted in a domino Michael addition-carbene rearrangement-cyclization reaction to produce directly tricyclic heterocycles in high yields, whereas the reaction with 2-mercaptobenzoxazole afforded 1-alkynyl sulfides. PMID:16220178

  4. Nearly degenerate isomers of C(BH)2: cumulene, carbene, or carbone?

    PubMed

    Barua, Shiblee R; Allen, Wesley D; Kraka, Elfi; Jerabek, Paul; Sure, Rebecca; Frenking, Gernot

    2013-11-18

    The ground electronic state of C(BH)2 exhibits both a linear minimum and a peculiar angle-deformation isomer with a central B-C-B angle near 90°. Definitive computations on these species and the intervening transition state have been executed by means of coupled-cluster theory including single and double excitations (CCSD), perturbative triples (CCSD(T)), and full triples with perturbative quadruples (CCSDT(Q)), in concert with series of correlation-consistent basis sets (cc-pVXZ, X=D, T, Q, 5, 6; cc-pCVXZ, X=T, Q). Final energies were pinpointed by focal-point analyses (FPA) targeting the complete basis-set limit of CCSDT(Q) theory with auxiliary core correlation, relativistic, and non-Born-Oppenheimer corrections. Isomerization of the linear species to the bent form has a minuscule FPA reaction energy of 0.02 kcal mol(-1) and a corresponding barrier of only 1.89 kcal mol(-1). Quantum tunneling computations reveal interconversion of the two isomers on a timescale much less than 1 s even at 0 K. Highly accurate CCSD(T)/cc-pVTZ and composite c~CCSDT(Q)/cc-pCVQZ anharmonic vibrational frequencies confirm matrix-isolation infrared bands previously assigned to linear C(BH)2 and provide excellent predictions for the heretofore unobserved bent isomer. Chemical bonding in the C(BH)2 species was exhaustively investigated by the atoms-in-molecules (AIM) approach, molecular orbital plots, various population analyses, local mode vibrations and force constants, unified reaction valley analysis (URVA), and other methods. Linear C(BH)2 is a cumulene, whereas bent C(BH)2 is best characterized as a carbene with little carbone character. Weak B-B attraction is clearly present in the unusual bent isomer, but its strength is insufficient to form a CB2 ring with a genuine boron-boron bond and attendant AIM bond path. PMID:24123325

  5. Efficient synthetic protocols for the preparation of common N-heterocyclic carbene precursors

    PubMed Central

    Hans, Morgan; Lorkowski, Jan; Demonceau, Albert

    2015-01-01

    Summary The one-pot condensation of glyoxal, two equivalents of cyclohexylamine, and paraformaldehyde in the presence of aqueous HBF4 provided a straightforward access to 1,3-dicyclohexylimidazolium tetrafluoroborate (ICy·HBF4). 1,3-Dibenzylimidazolium tetrafluoroborate (IBn·HBF4) was obtained along the same lines. To synthesize 1,3-diarylmidazolium salts, it was necessary to isolate the intermediate N,N'-diarylethylenediimines prior to their cyclization. Although this additional step required more time and reagents, it led to a much more efficient overall process. It also proved very convenient to carry out the synthesis of imidazolinium salts in parallel to their imidazolium counterparts via the reduction of the diimines into diammonium salts. The critical assembly of the C2 precarbenic unit was best achieved with paraformaldehyde and chlorotrimethylsilane in the case of imidazolium derivatives, whereas the use of triethyl orthoformate under microwave irradiation was most appropriate for the fast and efficient synthesis of imidazolinium salts. This strategy was applied to the synthesis of six common N-heterocyclic carbene precursors, namely, 1,3-dimesitylimidazolium chloride (IMes·HCl), 1,3-dimesitylimidazolium tetrafluoroborate (IMes·HBF4), 1,3-dimesitylimidazolinium chloride (SIMes·HCl), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IDip·HCl or IPr·HCl), 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride (SIDip·HCl or SIPr·HCl), and 1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazolium chloride (IDip*·HCl or IPr*·HCl).

  6. Electrochemiluminescent ruthenium(II) N-heterocyclic carbene complexes: a combined experimental and theoretical study.

    PubMed

    Barbante, Gregory J; Francis, Paul S; Hogan, Conor F; Kheradmand, Peyman R; Wilson, David J D; Barnard, Peter J

    2013-07-01

    A series of four Ru(II) complexes of the form [Ru(bpy)2(C(^)N)](2+) (where C(^)N is a bidentate pyridine-functionalized imidazolylidene- or benzimidazolylidene-based N-heterocyclic carbene (NHC) ligand and bpy is 2,2'-bipyridine) have been synthesized using a Ag(I) transmetalation protocol from the Ru(II) precursor compound, Ru(bpy)2Cl2. The synthesized azolium salts and Ru(II) complexes were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy, cyclic voltammetry, and electronic absorption and emission spectroscopy. The molecular structures for two benzimidazolium salts and three Ru(II) complexes were determined by single crystal X-ray diffraction. The complexes display photoluminescence within the range 611-629 nm, with the emission wavelength of the benzimidazolylidene containing structures, slightly blue-shifted relative to the imidazolylidene containing complexes. All complexes exhibited a reversible, one-electron oxidation, which is assigned to the Ru(2+/3+) redox couple. When compared to [Ru(bpy)3](2+), complexes of imidazolylidene containing ligands were oxidized at more negative potentials, while those of the benzimidazolylidene containing ligands were oxidized at more positive potentials. All four complexes exhibited moderately intense electrochemiluminescence (ECL) with the obtained ECL spectra closely resembling the photoluminescence spectra. The ability to predictably fine-tune the highest occupied molecular orbital (HOMO) level of the Ru(II) complexes via the flexible synthetic strategy offered by NHCs is valuable for the design of ECL-based multiplexed detection strategies. PMID:23772555

  7. Rhenium complexes of bidentate, bis-bidentate and tridentate N-heterocyclic carbene ligands.

    PubMed

    Chan, Chung Ying; Barnard, Peter J

    2015-11-28

    A series of eight Rhenium(i)-N-heterocyclic carbene (NHC) complexes of the general form [ReCl(CO)3(C^C)] (where C^C is a bis(NHC) bidentate ligand), [ReCl(CO)3(C^C)]2 (where C^C is a bis-bidentate tetra-NHC ligand) and [Re(CO)3(C^N^C)](+)[X](-) (where C^N^C is a bis(NHC)-amine ligand and the counter ion X is either the ReO4(-) or PF6(-)) have been synthesised using a Ag2O transmetallation protocol. The novel precursor imidazolium salts and Re(i) complexes were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for two imidazolium salt and six Re(i) complexes were determined by single crystal X-ray diffraction. These NHC ligand systems are of interest for possible applications in the development of Tc-99m or Re-186/188 radiopharmaceuticals and as such the stability of two complexes of the form [ReCl(CO)3(C^C)] and [Re(CO)3(C^N^C)][ReO4] were evaluated in ligand challenge experiments using the metal binding amino acids l-histidine or l-cysteine. These studies showed that the former was unstable, with the chloride ligand being replaced by either cysteine or histidine, while no evidence for transchelation was observed for the latter suggesting that bis(NHC)-amine ligands of this type may be suitable for biological applications. PMID:26477971

  8. Ruthenium and osmium complexes of dihydroperimidine-based N-heterocyclic carbene pincer ligands.

    PubMed

    McQueen, Caitlin M A; Hill, Anthony F; Ma, Chenxi; Ward, Jas S

    2015-12-21

    The reactions of N,N'-bis(phosphinomethyl)dihydroperimidine pro-ligands H2C(NCH2PR2)2C10H6 (R = Cy 1a, R = Ph 1b) with [RuCl2(PPh3)3] give markedly different products. Chelate-assisted double C-H activation in the former affords the perimidinylidene-based N-heterocyclic carbene (per-NHC) pincer complex [RuCl2(OC4H8){?(3)-P,C,P'-C(NCH2PCy2)2C10H6}] (2), while the latter reaction provides the asymmetric PNP-coordinated complex [RuCl2(PPh3){?(3)-P,N,P'-CH2(NCH2PPh2)2C10H6}] (3), in which no C-H activation has occurred. Subsequent reactions of the per-NHC complex 2 with carbon monoxide and mesityl isocyanide readily displaced the labile THF ligand to afford the complexes [RuCl2(CA){?(3)-P,C,P'-C(NCH2PCy2)2C10H6}] (A = O 4, A = NC6H2Me35). Double C-H activation of 1a and 1b was significantly more facile on reaction with [OsCl2(PPh3)3], providing the per-NHC complexes [OsHCl(PPh3){?(3)-P,C,P'-C(NCH2PR2)2C10H6}] (R = Cy 7a, R = Ph 7b, respectively), each as two isomers. The reactions of 1b with [Ru2(?-Cl)2Cl2(?-C6H3Me3)2] or [AuCl(THT)] (THT = tetrahydrothiophene) provide the bimetallic complexes [Ru2{?-H2C(NCH2PPh2)2C10H6}Cl4(?-C6H3Me3)2] (8) and [Au2{?-H2C(NCH2PPh2)2C10H6}Cl2] (9) without C-H activation occurring. PMID:26492361

  9. Twisted stable homotopy theory

    E-print Network

    Douglas, Christopher L

    2005-01-01

    There are two natural interpretations of a twist of stable homotopy theory. The first interpretation of a twist is as a nontrivial bundle whose fibre is the stable homotopy category. This kind of radical global twist forms ...

  10. Phosphorescent iridium(III)-bis-N-heterocyclic carbene complexes as mitochondria-targeted theranostic and photodynamic anticancer agents.

    PubMed

    Li, Yi; Tan, Cai-Ping; Zhang, Wei; He, Liang; Ji, Liang-Nian; Mao, Zong-Wan

    2015-01-01

    Mitochondria-targeted compounds represent a promising approach to target tumors selectively and overcome resistance to current anticancer therapies. In this work, three cyclometalated iridium(III) complexes (1-3) containing bis-N-heterocyclic carbene (NHC) ligands have been explored as theranostic and photodynamic agents targeting mitochondria. These complexes display rich photophysical properties, which greatly facilitates the study of their intracellular fate. All three complexes are more cytotoxic than cisplatin against the cancer cells screened. 1-3 can penetrate into human cervical carcinoma (HeLa) cells quickly and efficiently, and they can carry out theranostic functions by simultaneously inducing and monitoring the morphological changes in mitochondria. Mechanism studies show that these complexes exert their anticancer efficacy by initiating a cascade of events related to mitochondrial dysfunction. Additionally, they display up to 3 orders of magnitude higher cytotoxicity upon irradiation at 365 nm, which is so far the highest photocytotoxic responses reported for iridium complexes. PMID:25477176

  11. Grubbs-Hoveyda type catalysts bearing a dicationic N-heterocyclic carbene for biphasic olefin metathesis reactions in ionic liquids.

    PubMed

    Koy, Maximilian; Altmann, Hagen J; Autenrieth, Benjamin; Frey, Wolfgang; Buchmeiser, Michael R

    2015-01-01

    The novel dicationic metathesis catalyst [(RuCl2(H2ITapMe2)(=CH-2-(2-PrO)-C6H4))(2+) (OTf(-))2] (Ru-2, H2ITapMe2 = 1,3-bis(2',6'-dimethyl-4'-trimethylammoniumphenyl)-4,5-dihydroimidazol-2-ylidene, OTf(-) = CF3SO3 (-)) based on a dicationic N-heterocyclic carbene (NHC) ligand was prepared. The reactivity was tested in ring opening metathesis polymerization (ROMP) under biphasic conditions using a nonpolar organic solvent (toluene) and the ionic liquid (IL) 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM(+)][BF4 (-)]. The structure of Ru-2 was confirmed by single crystal X-ray analysis. PMID:26664582

  12. Grubbs–Hoveyda type catalysts bearing a dicationic N-heterocyclic carbene for biphasic olefin metathesis reactions in ionic liquids

    PubMed Central

    Koy, Maximilian; Altmann, Hagen J; Autenrieth, Benjamin; Frey, Wolfgang

    2015-01-01

    Summary The novel dicationic metathesis catalyst [(RuCl2(H2ITapMe2)(=CH–2-(2-PrO)-C6H4))2+ (OTf?)2] (Ru-2, H2ITapMe2 = 1,3-bis(2’,6’-dimethyl-4’-trimethylammoniumphenyl)-4,5-dihydroimidazol-2-ylidene, OTf? = CF3SO3 ?) based on a dicationic N-heterocyclic carbene (NHC) ligand was prepared. The reactivity was tested in ring opening metathesis polymerization (ROMP) under biphasic conditions using a nonpolar organic solvent (toluene) and the ionic liquid (IL) 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM+][BF4 ?]. The structure of Ru-2 was confirmed by single crystal X-ray analysis. PMID:26664582

  13. Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]- oct-6-ene ring systems.

    PubMed

    Munro, Kevin R; Male, Louise; Spencer, Neil; Grainger, Richard S

    2013-10-21

    ?-Hydroxyalkylidene carbenes, generated from thermolysis of ?,?-epoxy-N-aziridinylimines, undergo diastereotopic group selective 1,5 C–H insertion reactions on 2,4-dimethyl-8-oxabicyclo[3.2.1]oct-6-ene ring systems. Protection of a tertiary alcohol at C-3 of the bridged oxabicycle as a trimethylsilyl ether reverses the sense of diastereoselectivity. 1,5 C–H insertion into a methine adjacent to an OBn group, 1,5 O–R insertion into a tertiary alcohol (R = H) or silylether (R = TMS) at C-3 to form spirocyclic dihydrofurans, 1,2-rearrangement to an alkyne and fragmentation to a ketone are competing major pathways for 2-benzyloxy-substituted 8-oxabicyclo[3.2.1]oct-6-ene systems. Dihydrofuran formation is shown to be a result of substitution on the oxabicyclic ring system through comparison with other methods of alkylidene carbene formation. PMID:24175334

  14. C-H activation in Ir(III) and N-demethylation in Pt(II) complexes with mesoionic carbene ligands: examples of monometallic, homobimetallic and heterobimetallic complexes.

    PubMed

    Maity, Ramananda; Tichter, Tim; van der Meer, Margarethe; Sarkar, Biprajit

    2015-11-14

    Mononuclear Pt(II) and the first dinuclear Pt(II) complexes along with a cyclometalated heterobimetallic Ir(III)/Pd(II) complex bearing mesoionic carbene donor ligands are presented starting from the same bis-triazolium salt. The mononuclear Pt(II) complex possesses a free triazole moiety which is generated from the corresponding triazolium salt through an N-demethylation reaction, whereas the mononuclear Ir(III) complex features an unreacted triazolium unit. PMID:26443200

  15. Luminescent Ruthenium(II) Complex Bearing Bipyridine and N-Heterocyclic Carbene-based C?N?C Pincer Ligand for Live-Cell Imaging of Endocytosis

    PubMed Central

    Tsui, Wai-Kuen; Chung, Lai-Hon; Wong, Matthew Man-Kin; Tsang, Wai-Him; Lo, Hoi-Shing; Liu, Yaxiang; Leung, Chung-Hang; Ma, Dik-Lung; Chiu, Sung-Kay; Wong, Chun-Yuen

    2015-01-01

    Luminescent ruthenium(II)-cyanide complex with N-heterocyclic carbene pincer ligand C?N?C = 2,6-bis(1-butylimidazol-2-ylidene)pyridine and 2,2?-bipyridine (bpy) shows minimal cytotoxicity to both human breast carcinoma cell (MCF-7) and human retinal pigmented epithelium cell (RPE) in a wide range of concentration (0.1–500??M), and can be used for the luminescent imaging of endocytosis of the complex in these cells. PMID:25765974

  16. Synthesis of novel polysubstituted N-benzyl-1H-pyrroles via a cascade reaction of alkynyl Fischer carbenes with ?-imino glycine methyl esters.

    PubMed

    de la Cruz, Fabiola N; López, Julio; Jiménez-Halla, J Óscar C; Flores-Álamo, Marcos; Tamaríz, Joaquín; Delgado, Francisco; Vázquez, Miguel A

    2015-12-28

    An efficient and simple synthesis of novel and densely substituted N-benzyl-1H-pyrroles 6a-r is described by a 1,4-addition/isomerization/ring closure/demetalation cascade process of alkynyl Fischer carbene complexes 1a-f and 2a and ?-imino glycine methyl esters 3a, b, d, g, h, and k promoted with LDA. PMID:26488365

  17. Luminescent Ruthenium(II) Complex Bearing Bipyridine and N-Heterocyclic Carbene-based C?N?C Pincer Ligand for Live-Cell Imaging of Endocytosis

    NASA Astrophysics Data System (ADS)

    Tsui, Wai-Kuen; Chung, Lai-Hon; Wong, Matthew Man-Kin; Tsang, Wai-Him; Lo, Hoi-Shing; Liu, Yaxiang; Leung, Chung-Hang; Ma, Dik-Lung; Chiu, Sung-Kay; Wong, Chun-Yuen

    2015-03-01

    Luminescent ruthenium(II)-cyanide complex with N-heterocyclic carbene pincer ligand C?N?C = 2,6-bis(1-butylimidazol-2-ylidene)pyridine and 2,2'-bipyridine (bpy) shows minimal cytotoxicity to both human breast carcinoma cell (MCF-7) and human retinal pigmented epithelium cell (RPE) in a wide range of concentration (0.1-500 ?M), and can be used for the luminescent imaging of endocytosis of the complex in these cells.

  18. An Electronic Rationale for Observed Initiation Rates in Ruthenium-Mediated Olefin Metathesis: Charge Donation in Phosphine And N-Heterocyclic Carbene Ligands

    SciTech Connect

    Getty, K.; Delgado-Jaime, M.U.; Kennepohl, P.

    2009-06-01

    Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts.

  19. Nickel(0)/N-Heterocyclic Carbene-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of Two Enones and an Alkyne: Access to Cyclohexenes with Four Contiguous Stereogenic Centers.

    PubMed

    Kumar, Ravindra; Tokura, Hiromu; Nishimura, Akira; Mori, Tadashi; Hoshimoto, Yoichi; Ohashi, Masato; Ogoshi, Sensuke

    2015-12-18

    A nickel(0)/chiral N-heterocyclic carbene (NHC)-catalyzed fully intermolecular, enantioselective [2 + 2 + 2] cycloaddition of two enones and an alkyne has been developed to access enantioenriched cyclohexenes. A single diastereomer was obtained with a successive generation of four contiguous stereogenic centers. The absolute configuration of cyclohexene derivative 3aa was determined by X-ray diffraction and circular dichroism (CD) spectral studies. PMID:26618525

  20. The development and catalytic uses of N-heterocyclic carbene gold complexes.

    PubMed

    Nolan, Steven P

    2011-02-15

    Gold has emerged as a powerful synthetic tool in the chemist's arsenal. From the early use of inorganic salts such as AuCl and AuCl(3) as catalysts, the field has evolved to explore ligands that fine-tune reactivity, stability, and, more recently, selectivity in gold-mediated processes. Substrates generally contain alkenes or alkynes, and they usually involve straightforward protocols in air with solvents that can often times be of technical grade. The actual catalytic species is the putative cationic gold(I) complex [Au(L)](+) (where L is a phosphorus-based species or N-heterocyclic carbene, NHC). The early gold systems bearing phosphine and phosphite ligands provided important transformations and served as useful mechanistic probes. More recently, the use of NHCs as ligands for gold has rapidly gained in popularity. These two-electron donor ligands combine strong ?-donating properties with a steric profile that allows for both stabilization of the metal center and enhancement of its catalytic activity. As a result, the gold-NHC complexes have been used as well-defined precatalysts and have permitted the isolation of reactive single-component systems that are now used instead of the initial [Au(L)Cl]/silver salt method. Because some are now commercially available, NHC-containing gold(I) complexes are gathering increasing interest. In this Account, we describe the chronological development of this chemistry in our laboratories, highlighting the advantages of this family of gold complexes and reviewing their synthesis and applications in catalysis. We first outline the syntheses, which are straightforward. The complexes generally exhibit high stability, allowing for indefinite storage and easy handling. We next consider catalysis, particularly examining efficacy in cycloisomerization, other skeletal rearrangements, addition of water to alkynes and nitriles, and C-H bond activation. These processes are quite atom-economical, and in the most recent C-H reactions the only byproduct is water. State-of-the-art methodology now involves single-component catalysts, precluding the need for costly silver co-catalysts. Remarkably, the use of an NHC as a supporting ligand has permitted the isolation of [Au(L)(S)](+) species (where S is a solvent molecule such as a nitrile), which can act as single-component catalysts. Some improvements are still needed, as the single components are most often synthesized with a silver reagent. Owing to the stabilizing effect of NHC coordination, some NHC-containing systems can catalyze extremely challenging reactions (at temperatures as high as 140 °C) and react at very low loadings of gold (ppm levels). Our latest developments deal with C-H bond functionalization and hold great promise. We close with a selection of important developments by the community with gold-NHC complexes. As demonstrated by the turns and twists encountered during our own journey in the gold-NHC venture, the chemistry described here, combining fundamental organometallic, catalytic, and organic methodology, remains rich in opportunities, especially considering that only a handful of gold(I) architectures has been studied. We hope this Account will encourage young researchers to explore this emerging area, as the adage "the more you do, the more you have to do" surely holds true in gold-mediated catalysis. PMID:21028871

  1. Coinage-metal mediated ring opening of cis-1,2-dimethoxycyclopropane: trends from the gold, copper, and silver Fischer carbene bond strength.

    PubMed

    Batiste, Laurent; Chen, Peter

    2014-07-01

    N-heterocyclic carbene (NHC) supported coinage metal cations proved to react in the gas phase with the electron-rich cis-1,2-dimethoxycyclopropane. Upon Collision Induced Dissociation (CID), several spectrometric fragment-ion signals were observed, one corresponding to the recovery of the bare cation IMes-M(+) (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and the second to the methoxymethylidene metal complex IMes-M-[HCOCH3](+). The gold and copper complexes appear to stabilize the carbene sufficiently enough to promote the latter channel. On the contrary, the silver complex binds weakly to the methoxymethylidene moiety as observed by the predominance of the bare cation IMes-M(+) channel. Density Functional Theory (DFT) investigations of the Potential Energy Surface and Bond Energy Decomposition Analyses provided results that correlate well with the experimental data. In the case of the bare cation channel, two distinct reaction pathways were found: a straightforward decoordination of the cyclopropane and a cationic rearrangement of the three-membered ring into a dimethoxypropylene isomer before dissociation. However, for the abstraction of the methoxymethylidene moiety by the metal cation, only one pathway was found. In analogy to earlier studies by other groups, we found the trend Au > Cu > Ag for the metal-carbene bond strength. PMID:24911627

  2. INVERSE STABLE SUBORDINATORS.

    PubMed

    Meerschaert, Mark M; Straka, Peter

    2013-01-01

    The inverse stable subordinator provides a probability model for time-fractional differential equations, and leads to explicit solution formulae. This paper reviews properties of the inverse stable subordinator, and applications to a variety of problems in mathematics and physics. Several different governing equations for the inverse stable subordinator have been proposed in the literature. This paper also shows how these equations can be reconciled. PMID:25045216

  3. The Stable Pairing Problem

    ERIC Educational Resources Information Center

    Greenwell, Raymond N.; Seabold, Daniel E.

    2014-01-01

    The Gale-Shapley stable marriage theorem is a fascinating piece of twentieth-century mathematics that has many practical applications--from labor markets to school admissions--yet is accessible to secondary school mathematics students. David Gale and Lloyd Shapley were both mathematicians and economists who published their work on the Stable

  4. Nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in olefin metathesis: a computational study.

    PubMed

    Pazio, A; Wo?niak, K; Grela, K; Trzaskowski, B

    2015-11-18

    We used the density functional theory to evaluate the suitability of nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in ruthenium-based metathesis catalysts. We demonstrate that these analogues induce only minor structural changes in Hoveyda-Grubbs-like precatalysts, but have major impact on precatalyst initiation. Nitrenium ion-modified precatalysts are characterized by a weak Ru-N bond resulting in a relatively strong Ru-O bond and large free energy barriers for initiation, making them good candidates for efficient latent Ru-based catalysts. On the other hand the trivalent boron ligand, bearing a formal -1 charge, binds strongly to the ruthenium ion, weakening the Ru-O bond and facilitating its dissociation, to promote fast reaction initiation. We show that the calculated bond dissociation energy of the Ru-C/N/B bond may serve as an accurate indicator of the Ru-O bond strength and the rate of metathesis initiation. PMID:26525899

  5. A monotopic aluminum telluride with an Al=Te double bond stabilized by N-heterocyclic carbenes

    PubMed Central

    Franz, Daniel; Szilvási, Tibor; Irran, Elisabeth; Inoue, Shigeyoshi

    2015-01-01

    Aluminum chalcogenides are mostly encountered in the form of bulk aluminum oxides that are structurally diverse but typically consist of networks with high lattice energy in which the chalcogen atoms bridge the metal centres. This makes their molecular congeners difficult to synthesize because of a pronounced tendency for oligomerization. Here we describe the isolation of the monotopic aluminum chalcogenide (LDipN)AlTe(LEt)2 (LDip=1,3-(2,6-diisopropylphenyl)-imidazolin-2-imine, LEt=1,3-diethyl-4,5-dimethyl-imidazolin-2-ylidene). Unique features of (LDipN)AlTe(LEt)2 are the terminal position of the tellurium atom, the shortest aluminum–tellurium distance hitherto reported for a molecular complex and the highest bond order reported for an interaction between these elements, to the best of our knowledge. At elevated temperature (LDipN)AlTe(LEt)2 equilibrates with dimeric {(LDipN)AlTe(LEt)}2 in which the chalcogen atoms assume their common role as bridges between the metal centres. These findings demonstrate that (LDipN)AlTe(LEt)2 comprises the elusive Al=Te double bond in the form of an N-heterocyclic carbene-stabilized species. PMID:26612781

  6. A monotopic aluminum telluride with an Al=Te double bond stabilized by N-heterocyclic carbenes.

    PubMed

    Franz, Daniel; Szilvási, Tibor; Irran, Elisabeth; Inoue, Shigeyoshi

    2015-01-01

    Aluminum chalcogenides are mostly encountered in the form of bulk aluminum oxides that are structurally diverse but typically consist of networks with high lattice energy in which the chalcogen atoms bridge the metal centres. This makes their molecular congeners difficult to synthesize because of a pronounced tendency for oligomerization. Here we describe the isolation of the monotopic aluminum chalcogenide (L(Dip)N)AlTe(L(Et))2 (L(Dip)=1,3-(2,6-diisopropylphenyl)-imidazolin-2-imine, L(Et)=1,3-diethyl-4,5-dimethyl-imidazolin-2-ylidene). Unique features of (L(Dip)N)AlTe(L(Et))2 are the terminal position of the tellurium atom, the shortest aluminum-tellurium distance hitherto reported for a molecular complex and the highest bond order reported for an interaction between these elements, to the best of our knowledge. At elevated temperature (L(Dip)N)AlTe(L(Et))2 equilibrates with dimeric {(L(Dip)N)AlTe(L(Et))}2 in which the chalcogen atoms assume their common role as bridges between the metal centres. These findings demonstrate that (L(Dip)N)AlTe(L(Et))2 comprises the elusive Al=Te double bond in the form of an N-heterocyclic carbene-stabilized species. PMID:26612781

  7. From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates.

    PubMed

    Ottou, Winnie Nzahou; Bourichon, Damien; Vignolle, Joan; Wirotius, Anne-Laure; Robert, Fredéric; Landais, Yannick; Sotiropoulos, Jean-Marc; Miqueu, Karinne; Taton, Daniel

    2015-06-22

    Among various N-heterocyclic carbenes (NHCs) tested, only 1,3-bis(tert-butyl)imidazol-2-ylidene (NHC(tBu) ) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC-catalyzed 1,4-addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well-defined ?-alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N-dimethylformamide at 25?°C. A hydroxyl-terminated poly(ethylene oxide) (PEO-OH) macro-initiator was also employed to directly access PEO-b-PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC(tBu) . PMID:26013759

  8. Carbene-induced synthesis of the first borironium cations using the [(?(5)-C5Me5)Fe(CO)2](-) anion as an unlikely leaving group.

    PubMed

    Braunschweig, Holger; Dewhurst, Rian D; Ferkinghoff, Katharina

    2015-12-15

    Reaction of N-heterocyclic carbenes with ferroborirene complex [{(?(5)-C5Me5)Fe(CO)2}{BC2(SiMe3)2}] results in heterolytic Fe-B bond cleavage, yielding borironium ions, a new class of boron-containing heterocycles. The reaction rests on the surprising ability of the reactive [(?(5)-C5Me5)Fe(CO)2](-) anion to act as a leaving group. The properties of these species were investigated by multinuclear NMR spectroscopy, as well as single-crystal X-ray diffraction. PMID:26511336

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

    PubMed

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

    2015-11-01

    Ruthenium chemistry and applications in catalytic olefin metathesis based on N-phosphino-functionalized N-heterocyclic carbene ligands (NHCPs) are presented. Alkyl NHCP Ru coordination chemistry is described, and access to several potential synthetic precursors for ruthenium alkylidene complexes is outlined, incorporating both trimethylsilyl and phenyl alkylidenes. The Ru alkylidene complexes are evaluated as potential olefin metathesis catalysts and were shown to behave in a latent fashion. They displayed catalytic activity at elevated temperatures for both ring closing metathesis and ring opening metathesis polymerization. PMID:26479425

  10. Highly Stable Microwave Resonator

    NASA Technical Reports Server (NTRS)

    Strayer, Donald M.; Thakoor, Sarita; Dick, G. John; Mercereau, James E.

    1987-01-01

    Superconducting walls on sapphire-filled cavity make low-loss device. Improved microwave resonant cavity consists of sapphire cylinder coated with thin film of superconducting lead. Operated well below superconducting transition temperature at 1.5K, cavity demonstrated superior frequency stability and quality factor. Cavity frequency highly stable and therefore suitable for use in standard frequency generators and filters.

  11. Stable isotope studies

    SciTech Connect

    Ishida, T.

    1992-01-01

    The research has been in four general areas: (1) correlation of isotope effects with molecular forces and molecular structures, (2) correlation of zero-point energy and its isotope effects with molecular structure and molecular forces, (3) vapor pressure isotope effects, and (4) fractionation of stable isotopes. 73 refs, 38 figs, 29 tabs.

  12. On the Relationship between the Enthalpy of Formation of Carbenes upon Cleavage of the Double Bond in Fluoroolefins and the Electron Density on the pi Bond: An Ab Initio Study

    SciTech Connect

    Borisov, Yurii A.; Garrett, Bruce C.; Kobanovskii, Y. A.; Bilera, I. V.; Buravtsev, N. N.

    2003-08-07

    In this study, we established a correlation between the enthalpy of cleavage of the C=C bond in fluorine-substituted olefins giving rise to two carbenes in the electronic ground state and the distribution of the electron density on this bond.

  13. Synthesis of Well-Defined Copper "N"-Heterocyclic Carbene Complexes and Their Use as Catalysts for a "Click Reaction": A Multistep Experiment that Emphasizes the Role of Catalysis in Green Chemistry

    ERIC Educational Resources Information Center

    Ison, Elon A.; Ison, Ana

    2012-01-01

    A multistep experiment for an advanced synthesis lab course that incorporates topics in organic-inorganic synthesis and catalysis and highlights green chemistry principles was developed. Students synthesized two "N"-heterocyclic carbene ligands, used them to prepare two well-defined copper(I) complexes and subsequently utilized the complexes as…

  14. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    SciTech Connect

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady; Sadow, Aaron D

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(?4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(?4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(?4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(?4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(?-Cl)(?2-C8H14)2]2 (M = Rh, Ir) provide {?4-PhB(OxMe2)2ImMes?CH2}Rh(?-H)(?-Cl)Rh(?2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(?3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {?4-PhB(OxMe2)2ImMes?CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis-[Ir](H)(Ph) complex. Alternatively, the rhodium carbonyl 5 or iridium isocyanide {PhB(OxMe2)2ImMes}Ir(CO)CNtBu (15) reacts with PhSiH3 in the dark to form the silyl compound {PhB(OxMe2)2ImMes}RhH(SiH2Ph)CO (14) or {PhB(OxMe2)2ImMes}IrH(SiH2Ph)CNtBu (17). These examples demonstrate the enhanced thermal reactivity of {PhB(OxMe2)2ImMes}-supported iridium and rhodium carbonyl compounds in comparison to tris(oxazolinyl)borate, tris(pyrazolyl)borate, and cyclopentadienyl-supported compounds.

  15. Chemistry of N,S-Heterocyclic Carbene and Metallaboratrane Complexes: A New ?(3) -BCC-Borataallyl Complex.

    PubMed

    Roy, Dipak Kumar; De, Anangsha; Panda, Subhankar; Varghese, Babu; Ghosh, Sundargopal

    2015-09-21

    A high-yielding synthetic route for the preparation of group?9 metallaboratrane complexes [Cp*MBH(L)2 ], 1 and 2 (1, M=Rh, 2, M=Ir; L=C7 H4 NS2 ) has been developed using [{Cp*MCl2 }2 ] as precursor. This method also permitted the synthesis of an Rh-N,S-heterocyclic carbene complex, [(Cp*Rh)(L2 )(1-benzothiazol-2-ylidene)] (3; L=C7 H4 NS2 ) in good yield. The reaction of compound 3 with neutral borane reagents led to the isolation of a novel borataallyl complex [Cp*Rh(L)2 B{CH2 C(CO2 Me)}] (4; L=C7 H4 NS2 ). Compound 4 features a rare ?(3) -interaction between rhodium and the B-C-C unit of a vinylborane moiety. Furthermore, with the objective of generating metallaboratranes of other early and late transition metals through a transmetallation approach, reactions of rhoda- and irida-boratrane complexes with metal carbonyl compounds were carried out. Although the objective of isolating such complexes was not achieved, several interesting mixed-metal complexes [{Cp*Rh}{Re(CO)3 }(C7 H4 NS2 )3 ] (5), [Cp*Rh{Fe2 (CO)6 }(?-CO)S] (6), and [Cp*RhBH(L)2 W(CO)5 ] (7; L=C7 H4 NS2 ) have been isolated. All of the new compounds have been characterized in solution by mass spectrometry, IR spectroscopy, and (1) H, (11) B, and (13) C?NMR spectroscopies, and the structural types of 4-7 have been unequivocally established by crystallographic analysis. PMID:26251213

  16. gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors.

    PubMed

    Hu, Mingyou; Ni, Chuanfa; Li, Lingchun; Han, Yongxin; Hu, Jinbo

    2015-11-18

    A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis. PMID:26501359

  17. Stable glow discharge detector

    DOEpatents

    Koo, Jackson C.; Yu, Conrad M.

    2004-05-18

    A highly sensitive electronic ion cell for the measurement of trace elements in He carrier gas which involves glow discharge. A constant wave (CW) stable glow discharge detector which is controlled through a biased resistor, can detect the change of electron density caused by impurities in the He carrier gas by many orders of magnitude larger than that caused by direct ionization or electron capture. The stable glow discharge detector utilizes a floating pseudo-electrode to form a probe in or near the plasma and a solid rod electrode. By using this probe, the large variation of electron density due to trace amounts of impurities can be directly measured. The solid rod electrode provides greater stability and thus easier alignment.

  18. Stable isotopes in mineralogy

    USGS Publications Warehouse

    O'Neil, J.R.

    1977-01-01

    Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions. ?? 1977 Springer-Verlag.

  19. Stable local oscillator module.

    SciTech Connect

    Brocato, Robert Wesley

    2007-11-01

    This report gives a description of the development of a Stable Local Oscillator (StaLO) multi-chip module (MCM). It is a follow-on report to SAND2006-6414, Stable Local Oscillator Microcircuit. The StaLO accepts a 100MHz input signal and produces output signals at 1.2, 3.3, and 3.6 GHz. The circuit is built as a multi-chip module (MCM), since it makes use of integrated circuit technologies in silicon and lithium niobate as well as discrete passive components. This report describes the development of an MCM-based version of the complete StaLO, fabricated on an alumina thick film hybrid substrate.

  20. Thermally stable laminating resins

    NASA Technical Reports Server (NTRS)

    Jones, R. J.; Vaughan, R. W.; Burns, E. A.

    1972-01-01

    Improved thermally stable laminating resins were developed based on the addition-type pyrolytic polymerization. Detailed monomer and polymer synthesis and characterization studies identified formulations which facilitate press molding processing and autoclave fabrication of glass and graphite fiber reinforced composites. A specific resin formulation, termed P10P was utilized to prepare a Courtaulds HMS reinforced simulated airfoil demonstration part by an autoclave molding process.

  1. Spectroscopic characterization of triplet (2- and 3-thienyl)carbenes and development, implementation, and testing of a web-based tool for use in middle and high school classrooms

    NASA Astrophysics Data System (ADS)

    Pharr, Caroline Rebecca

    Photolysis (lambda> 543 nm) of 3-thienyldiazomethane (1) yields triplet s-Z and s-E 3-thienylcarbene (s-E 5 and s- Z 5), as characterized by IR, UV/vis, and EPR spectroscopy. The EPR spectra of s-E 5 and s-Z 5 are markedly different, and proved to be unusual. NBO calculations and a Mulliken spin density analysis were carried out to explore the complex nature of these spectra. In an effort to obtain a comparison to the unusual EPR spectra of 3-thienylcarbene and to explore how the photochemistry of the system would be perturbed, methyl and deuteriomethyl analogs of the parent compounds were studied. Photolysis (lambda> 534 nm) of 3-thienyl-1-diazoethane (16) yields only one triplet 3-thienylethylidene rotamer (s-E 21), as characterized by UV/vis, and EPR spectroscopy. EPR and UV/visible signals attributed to s-E 21 decreased by approximately 50% after sitting in the dark for 3.5 days, suggesting a "thermal" reaction at 10 K. Photolysis (lambda > 534 nm) of 3-thienyl-1-diazoethane- d3 (16-d3) yields triplet s-E 3-thienylcarbene-d3 (s-E 21-d3), as characterized by IR, UV/vis, and EPR spectroscopy. Analogous to the photochemistry of 16, s-Z 21 -d3 was absent from the matrix. s- E 21-d3 is thermally stable at 10 K. Our attempts at isolating a 2-thienylsubstituted triplet carbene in this family had been unsuccessful up to this point. Spectroscopic detection of a 2-thienylcarbene derivative was realized with the characterization of 2-benzo[b]thienylethylidene (34) and 2-benzo[b]thienylethylidene-d3 (34-d3) by IR, UV/vis, and EPR spectroscopy. The development and implementation of "Today's Science for Tomorrow's Scientist" (TSTS), a Web site that presents current science research in a format suitable for middle school and high school classrooms is discussed. The information presented on TSTS correlates with the National Science Education Standards, allowing for ease of use by teachers. TSTS was beta tested and then fully implemented in middle schools and high schools in the Madison, WI area. The data show that both middle school and high school students improve by a significant amount from content pre survey to content post survey after viewing TSTS.

  2. Stable crystalline annulated diaminocarbenes: coordination with rhodium(I), iridium(I) and catalytic hydroformylation studies.

    PubMed

    Dastgir, Sarim; Coleman, Karl S; Cowley, Andrew R; Green, Malcolm L H

    2009-09-21

    Stable annulated diaminocarbene ligands 7,9-bis(2,4,6-trimethylphenyl)-6b,9a-dihydroace naphtha[1,2-d]imidazolin-2-ylidene and 7,9-bis(2,6-diisopropylphenyl)-6b,9a-dihydroacenaphtho[1,2-d]imidazolin-2-ylidene; designated as (BIAN-SIMes, 5a,) and (BIAN-SIPr, 5b), respectively, have been prepared. The base dependent decomposition of imidazolinium salts via ring opening at the backbone was also observed. The corresponding rhodium(I) and iridum(I) complexes (4-1,5-COD)M(BIAN-SIMes)Cl and (4-1,5-COD)M(BIAN-SIPr)Cl; M= Rh (6a, 6b) and Ir (7a, 7b) have been synthesised by the reaction of free carbene with [M(4-1,5-COD)(-Cl)]2; where M= Rh, Ir. The cationic Ir(I) complexes [(4-1,5-COD)Ir(BIAN-SIMes)Py]BF4 8a and [(4-1,5-COD)Ir(BIAN -SIPr)Py]PF6 8b have also been synthesised. Compounds 4b, 5a, 6a, 6b, 7b and 8b have been structurally characterised. The catalytic activities for the rhodium(I) complexes 6a and 6b were evaluated for the hydroformylation of 1-octene. PMID:20449164

  3. Bi-stable optical actuator

    DOEpatents

    Holdener, Fred R. (Tracy, CA); Boyd, Robert D. (Livermore, CA)

    2000-01-01

    The present invention is a bi-stable optical actuator device that is depowered in both stable positions. A bearing is used to transfer motion and smoothly transition from one state to another. The optical actuator device may be maintained in a stable position either by gravity or a restraining device.

  4. Stable local oscillator microcircuit.

    SciTech Connect

    Brocato, Robert Wesley

    2006-10-01

    This report gives a description of the development of a Stable Local Oscillator (StaLO) Microcircuit. The StaLO accepts a 100MHz input signal and produces output signals at 1.2, 3.3, and 3.6 GHz. The circuit is built as a multi-chip module (MCM), since it makes use of integrated circuit technologies in silicon and lithium niobate as well as discrete passive components. The StaLO uses a comb generator followed by surface acoustic wave (SAW) filters. The comb generator creates a set of harmonic components of the 100MHz input signal. The SAW filters are narrow bandpass filters that are used to select the desired component and reject all others. The resulting circuit has very low sideband power levels and low phase noise (both less than -40dBc) that is limited primarily by the phase noise level of the input signal.

  5. Stable Magnetic Universes Revisited

    E-print Network

    Tayebeh Tahamtan; Mustafa Halilsoy

    2011-06-29

    A regular class of static, cylindrically symmetric pure magnetic field metrics is rederived in a different metric ansatz in all dimensions. Radial, time dependent perturbations show that for dimensions d>3 such spacetimes are stable at both near r\\approx0 and large radius r\\rightarrow\\infty. In a different gauge these stability analysis and similar results were known beforehand. For d=3, however, simultaneous stability requirement at both, near and far radial distances can not be reconciled for time - dependent perturbations. Restricted, numerical geodesics for neutral particles reveal a confinement around the center in the polar plane. Charged, time-like geodesics for d=4 on the other hand are shown numerically to run toward infinity.

  6. Stable umbral chromospheric structures

    NASA Astrophysics Data System (ADS)

    Henriques, V. M. J.; Scullion, E.; Mathioudakis, M.; Kiselman, D.; Gallagher, P. T.; Keenan, F. P.

    2015-02-01

    Aims: We seek to understand the morphology of the chromosphere in sunspot umbra. We investigate if the horizontal structures observed in the spectral core of the Ca II H line are ephemeral visuals caused by the shock dynamics of more stable structures, and examine their relationship with observables in the H-alpha line. Methods: Filtergrams in the core of the Ca II H and H-alpha lines as observed with the Swedish 1-m Solar Telescope are employed. We utilise a technique that creates composite images and tracks the flash propagation horizontally. Results: We find 0.?15 wide horizontal structures, in all of the three target sunspots, for every flash where the seeing is moderate to good. Discrete dark structures are identified that are stable for at least two umbral flashes, as well as systems of structures that live for up to 24 min. We find cases of extremely extended structures with similar stability, with one such structure showing an extent of 5''. Some of these structures have a correspondence in H-alpha, but we were unable to find a one-to-one correspondence for every occurrence. If the dark streaks are formed at the same heights as umbral flashes, there are systems of structures with strong departures from the vertical for all three analysed sunspots. Conclusions: Long-lived Ca II H filamentary horizontal structures are a common and likely ever-present feature in the umbra of sunspots. If the magnetic field in the chromosphere of the umbra is indeed aligned with the structures, then the present theoretical understanding of the typical umbra needs to be revisited. Movies associated to Figs. 3 and 4 are available in electronic form at http://www.aanda.org

  7. Stable superstring relics

    SciTech Connect

    Chang, S.; Coriano, C.; Faraggi, A.E. |

    1996-05-15

    The authors investigate the cosmological constraints on exotic stable matter states which arise in realistic free fermionic superstring models. These states appear in the superstring models due to a ``Wilson-line`` breaking of the unifying non-Abelian gauge symmetry. In the models that they consider the unifying SO(10) gauge symmetry is broken at the string level to SO(6) x SO(4), SU(5) x U(1) or SU(3) x SU(2) x U(1). The exotic matter states are classified according to the patterns of the SO(10) symmetry breaking. In SO(6) x XO(4) and SU(5) x U(1) type models one obtains fractionally charged states with Q{sub e.m.} = {+-}1/2. In SU(3) x SU(2) x U(1) type models one also obtains states with the regular charges under the Standard Model gauge group but with ``fractional`` charges under the U(1){sub z{prime}} symmetry. These states include down-like color triplets and electroweak doublets, as well as states which are Standard Model singlets. By analyzing the renormalizable and nonrenormalizable terms of the superpotential in a specific superstring model, the authors show that these exotic states can be stable. They investigate the cosmological constraints on the masses and relic density of the exotic states. They propose that, while the abundance and the masses of the fractionally charged states are highly constrained, the Standard Model-like states, and in particular the Standard Model singlet, are good dark matter candidates.

  8. Construct validity of Stable-2000 and Stable-2007 scores.

    PubMed

    Nunes, Kevin L; Babchishin, Kelly M

    2012-02-01

    We addressed the construct validity of Stable-2000 and Stable-2007 scores by examining correlations between selected items and validated independent measures of relevant constructs in samples of convicted sex offenders. In Study 1, the Child Molester Attitudes item of the Stable-2000 shared 23% of the variance with a self-report measure of beliefs supportive of child molestation, r(19) = .48. The Deviant Sexual Interests items of the Stable-2000 and Stable-2007 shared 7% to 66% of the variance, respectively, with an offense-history-based measure of pedophilic interests, r(18) = .27 for the Stable-2000 and r(11) = .81 for the Stable-2007. In Study 2, the Lovers/Intimate Partners, General Social Rejection/Loneliness, Rapist Attitudes, and Child Molester Attitudes items of the Stable-2000 shared 4% to 19% of the variance with self-report measures of, respectively, intimacy, r(90) = -.44; loneliness, r(88) = .34; beliefs supportive of rape, r(72) = .21; and beliefs supportive of child molestation, r(78) = .36. The results generally suggest that the Stable items examined are associated with measures of similar constructs; however, the degree of convergence was lower than expected. More systematic and comprehensive research is needed to examine convergence of the Stable items with other relevant measures and additional aspects of construct validity. Such efforts will provide a clearer understanding of dynamic risk factors, appropriate areas of focus for treatment efforts, and, more generally, why some sex offenders recidivate. PMID:21543623

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

    PubMed

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

    2013-05-28

    Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes affect the metal environment and therefore the related catalytic behaviour. Bearing in mind that there is a significant structural difference between both ligands in different olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. PMID:23455458

  10. H-D exchange in metal carbene complexes: Structure of cluster (?-H)(?-OCD3)Os3(CO)9{:C(CD3)NC2H8O}

    NASA Astrophysics Data System (ADS)

    Savkov, Boris; Maksakov, Vladimir; Kuratieva, Natalia

    2015-10-01

    X-ray and spectroscopic data for the new complex (?-H)(?-OCH3)Os3(CO)9{:C(CD3)NC2H8O} (2) obtained in the reaction of the (?-H)(?-Cl)Os3(CO)9{:C(CH3)NC2H8O} (1) with NaOCD3 in CD3OD solution are reported. It is shown that cluster 1 has the property of CH-acidity inherent of Fisher type carbenes. This had demonstrated using hydrogen deuterium exchange reaction in the presence of a strong base. Bridging chlorine to metoxide ligand substitution takes place during the reaction. The molecular structure of 2 is compared with known analogues.

  11. Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0(2,6)]decane.

    PubMed

    Hudzik, Jason M; Castillo, Álvaro; Bozzelli, Joseph W

    2015-09-24

    Exo-tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is an interesting strained ring compound and the single-component high-energy density hydrocarbon fuel known as JP-10. Important initial reactions of TCD at high temperatures could cleave a strained carbon-carbon (C-C) bond in the ring system creating diradicals also constrained by the remaining ring system. This study determines the thermochemical properties of these diradicals (TCD-H2 mJ-nJ where m and n correspond to the cleaved carbons sites) including the carbon-carbon bond dissociation energy (C-C BDE) corresponding to the cleaved TCD site. Thermochemical properties including enthalpies (?H°f298), entropies (S(T)), heat capacities (Cp(T)), and C-H and C-C BDEs for the parent (TCD-H2 m-n), radical (TCD-H2 mJ-n and m-nJ), diradical (TCD-H2 mJ-nJ), and carbene (TCD-H2 mJJ-n and m-nJJ) species are determined. Structures, vibrational frequencies, moments of inertia, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level of theory. Standard enthalpies of formation in the gas phase for the TCD-H2 m-n parent and radical species are determined using the B3LYP density functional theory and the higher level G3MP2B3 and CBS-QB3 composite methods. For singlet and triplet TCD diradicals and carbenes, M06-2X, ?B97X-D, and CCSD(T) methods are included in the analysis to determine ?H°f298 values. The C-C BDEs are further calculated using CASMP2(2,2)/aug-cc-pvtz//CASSCF(2,2)/cc-pvtz and with the CASMP2 energies extrapolated to the complete basis set limit. The bond energies calculated with these methods are shown to be comparable to the other calculation methods. Isodesmic work reactions are used for enthalpy analysis of these compounds for effective cancelation of systematic errors arising from ring strain. C-C BDEs range from 77.4 to 84.6 kcal mol(-1) for TCD diradical singlet species. C-H BDEs for the parent TCD-H2 m-n carbon sites range from 93 to 101 kcal mol(-1) with a similar range seen for loss of the second hydrogen to generate the diradical singlet species. A wider range for C-C BDEs is seen for the carbenes from about 77 to 100 kcal mol(-1) as compared to the diradicals. Results from the DFT methods for the parents, radicals, diradicals, and carbenes are in good agreement with results from the composite methods using our sets of work reactions. PMID:26295335

  12. NHC carbene supported half-sandwich hydridosilyl complexes of ruthenium: the impact of supporting ligands on SiH interligand interactions.

    PubMed

    Mai, Van Hung; Kuzmina, Lyudmila G; Churakov, Andrei V; Korobkov, Ilia; Howard, Judith A K; Nikonov, Georgii I

    2015-12-14

    Reaction of complex [CpRu(pyr)3][PF6] () with the NHC carbene IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) results in the NHC complex [Cp(IPr)Ru(pyr)2][PF6] (), which was studied by NMR specroscopy and X-ray diffraction analysis. Reaction of [Cp(IPr)Ru(pyr)2][PF6] () with LiAlH4 leads to the trihydride Cp(IPr)RuH3 () characterised by spectroscopic methods. Heating compound with hydrosilanes gives the dihydrido silyl derivatives Cp(IPr)RuH2(SiR3) (). Systematic X-ray diffraction studies suggest that complexes have stronger interligand SiH interactions than the isolobal phosphine complexes Cp(Pr3P)RuH2(SiR3). PMID:26599264

  13. Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene-Isoquinoline Complex

    SciTech Connect

    Thoi, VanSara; Kornienko, Nick; Margarit, C; Yang, Peidong; Chang, Christopher

    2013-06-07

    The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

  14. Visible-light photoredox catalysis: selective reduction of carbon dioxide to carbon monoxide by a nickel N-heterocyclic carbene-isoquinoline complex.

    PubMed

    Thoi, V Sara; Kornienko, Nikolay; Margarit, Charles G; Yang, Peidong; Chang, Christopher J

    2013-09-25

    The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene-amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni((Pr)bimiq1)](2+) (1c, where (Pr)bimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (E(cat) = -1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s(-1), respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion. PMID:24033186

  15. II. Stable sets and colourings 1. Stable sets and colourings

    E-print Network

    Schrijver, Alexander

    vertex set E and edge set {{e, f} | e, f E, e = f, ef = }. 1 #12;Well-known is the four-colourII. Stable sets and colourings 1. Stable sets and colourings Let G = (V, E) be a graph. A stable set is a subset S of V containing no edge of G. A clique is a subset C of V such that any two vertices

  16. Tris(carbene)borate ligands featuring imidazole-2-ylidene, benzimidazol-2-ylidene and 1,3,4-triazol-2-ylidene donors. Evaluation of donor properties in four-coordinate {NiNO}10 complexes

    PubMed Central

    Muñoz, Salvador B.; Foster, Wallace K.; Lin, Hsiu-Jung; Margarit, Charles G.; Dickie, Diane A.

    2012-01-01

    The synthesis and characterization of new tris(carbene)borate ligand precursors containing substituted benzimidazol-2-ylidene and 1,3,4-triazol-2-ylidene donor groups, as well as a new tris(imidazol-2-ylidene)borate ligand precursor are reported. The relative donor strength of the tris(carbene)borate ligands have been evaluated by the position of ?(NO) in four-coordinate {NiNO}10 complexes, and follows the order: imidazol-2-ylidene > benzimidazol-2-ylidene > 1,3,4-triazol-2-ylidene. There is a large variation in ?(NO), suggesting these ligands to have a wide range of donor strengths while maintaining a consistent ligand topology. All ligands are stronger donors than Tp* and Cp*. PMID:23140462

  17. Stable Anisotropic Materials.

    PubMed

    Li, Yijing; Barbic, Jernej

    2015-10-01

    The Finite Element Method (FEM) is commonly used to simulate isotropic deformable objects in computer graphics. Several applications (wood, plants, muscles) require modeling the directional dependence of the material elastic properties in three orthogonal directions. We investigate linear orthotropic materials, a special class of linear anisotropic materials where the shear stresses are decoupled from normal stresses, as well as general linear (non-orthotropic) anisotropic materials. Orthotropic materials generalize transversely isotropic materials, by exhibiting different stiffness in three orthogonal directions. Orthotropic materials are, however, parameterized by nine values that are difficult to tune in practice, as poorly adjusted settings easily lead to simulation instabilities. We present a user-friendly approach to setting these parameters that is guaranteed to be stable. Our approach is intuitive as it extends the familiar intuition known from isotropic materials. Similarly to linear orthotropic materials, we also derive a stability condition for a subset of general linear anisotropic materials, and give intuitive approaches to tuning them. In order to simulate large deformations, we augment linear corotational FEM simulations with our orthotropic and general anisotropic materials. PMID:26340037

  18. Stable face representations

    PubMed Central

    Jenkins, Rob; Burton, A. Mike

    2011-01-01

    Photographs are often used to establish the identity of an individual or to verify that they are who they claim to be. Yet, recent research shows that it is surprisingly difficult to match a photo to a face. Neither humans nor machines can perform this task reliably. Although human perceivers are good at matching familiar faces, performance with unfamiliar faces is strikingly poor. The situation is no better for automatic face recognition systems. In practical settings, automatic systems have been consistently disappointing. In this review, we suggest that failure to distinguish between familiar and unfamiliar face processing has led to unrealistic expectations about face identification in applied settings. We also argue that a photograph is not necessarily a reliable indicator of facial appearance, and develop our proposal that summary statistics can provide more stable face representations. In particular, we show that image averaging stabilizes facial appearance by diluting aspects of the image that vary between snapshots of the same person. We review evidence that the resulting images can outperform photographs in both behavioural experiments and computer simulations, and outline promising directions for future research. PMID:21536553

  19. Is our vacuum stable?

    E-print Network

    E. I. Guendelman; J. Portnoy

    2000-04-04

    The stability of our vacuum is analyzed and several aspects concerning this question are reviewed. 1) In the standard Glashow-Weinberg-Salam (GWS) model we review the instability towards the formation of a bubble of lower energy density and how the rate of such bubble formation process compares with the age of the Universe for the known values of the GWS model. 2) We also review the recent work by one of us (E.I.G) concerning the vacuum instability question in the context of a model that solves the cosmological constant problem. It turns out that in such model the same physics that solves the cosmological constant problem makes the vacuum stable. 3) We review our recent work concerning the instability of elementary particle embedded in our vacuum, towards the formation of an infinite Universe. Such process is not catastrophic. It leads to a "bifurcation type" instability in which our Universe is not eaten by a bubble (instead a baby universe is born). This universe does not replace our Universe rather it disconnects from it (via a wormhole) after formation.

  20. Do stable atmospheric layers exist?

    NASA Astrophysics Data System (ADS)

    Lovejoy, S.; Tuck, A. F.; Hovde, S. J.; Schertzer, D.

    2008-01-01

    The notion of stable atmospheric layers is a classical idealization used for understanding atmospheric dynamics and thermodynamics. Using state of the art drop sonde data and using conditional, dynamical and convective stability criteria we show that apparently stable layers are typically composed of a hierarchy of unstable layers themselves with embedded stable sublayers, and unstable sub-sub layers etc. i.e. in a Russian Matryoshka doll-like fractal hierarchy. We therefore argue that the notion of stable atmospheric layers is untenable and must be replaced by modern scaling notions.

  1. Stable isotope laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Becker, J. F.; Yaldaei, Ramil; Mckay, Christopher P.

    1989-01-01

    Recent advances in semiconductor laser technology have produced a reliable lightweight device ideally suited for a spacecraft high resolution molecular spectrometer. Lead-salt tunable diode lasers (TDL) emit in several spectral modes, each with a very narrow linewidth of -0.0003/cm. This spectral resolution is much narrower than typical Doppler broadened molecular linewidths in the mid-IR range. Thus it is possible to detect individual rotational lines within the vibrational band and measure their intensity, which can be used to determine gas concentration. The narrow spectral lines of any impurity gas tend to lie between the narrow lines of the gas of interest. This represents a major advantage over the accepted gas chromatograph mass spectrometer (GCMS) technique for measuring gas concentrations and isotope ratios. The careful and extensive gas purification procedures required to remove impurities for reliable GCMS measurements will not be required for an IR laser gas analysis. The infrared laser gas analysis technique is being developed to measure stable isotopic ratios of gases such as CO2, CH4, N2O, and NH3. This will eventually lead to development of instruments capable of in situ istopic measurements on planets such as Mars. The carbon (C-12, C-13) isotope ratio is indicative of the type of carbon fixation mechanisms (e.g., photosynthesis, respiration) in operation on a planet, while the nitrogen (N-14, N-15) isotope ratio can probably be used to date nitrogen-bearing Martian samples. The absorbance ratio of two adjacent lines of CO2 in the 2300/cm (4.3 micron) region of the spectrum was measured. The precision of the measurement is presently better than 1 percent and significant improvement is anticipated as rapid sweep-integration techniques and computer controlled data acquistion capabilities are incorporated.

  2. Stable isotope laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Becker, J. F.; Yaldaei, Ramil; McKay, Christopher P.

    1989-03-01

    Recent advances in semiconductor laser technology have produced a reliable lightweight device ideally suited for a spacecraft high resolution molecular spectrometer. Lead-salt tunable diode lasers (TDL) emit in several spectral modes, each with a very narrow linewidth of -0.0003/cm. This spectral resolution is much narrower than typical Doppler broadened molecular linewidths in the mid-IR range. Thus it is possible to detect individual rotational lines within the vibrational band and measure their intensity, which can be used to determine gas concentration. The narrow spectral lines of any impurity gas tend to lie between the narrow lines of the gas of interest. This represents a major advantage over the accepted gas chromatograph mass spectrometer (GCMS) technique for measuring gas concentrations and isotope ratios. The careful and extensive gas purification procedures required to remove impurities for reliable GCMS measurements will not be required for an IR laser gas analysis. The infrared laser gas analysis technique is being developed to measure stable isotopic ratios of gases such as CO2, CH4, N2O, and NH3. This will eventually lead to development of instruments capable of in situ istopic measurements on planets such as Mars. The carbon (C-12, C-13) isotope ratio is indicative of the type of carbon fixation mechanisms (e.g., photosynthesis, respiration) in operation on a planet, while the nitrogen (N-14, N-15) isotope ratio can probably be used to date nitrogen-bearing Martian samples. The absorbance ratio of two adjacent lines of CO2 in the 2300/cm (4.3 micron) region of the spectrum was measured. The precision of the measurement is presently better than 1 percent and significant improvement is anticipated as rapid sweep-integration techniques and computer controlled data acquistion capabilities are incorporated.

  3. A Stable Massive Charged Particle

    E-print Network

    G. Rajasekaran

    2011-06-08

    We consider the possibility of the existence of a stable massive charged particle by a minimal extension of the standard model particle content. Absolute stability in the case of singly charged particle is not possible if the usual doublet Higgs exists, unless a discrete symmetry is imposed.But a doubly charged particle is absolutely stable.

  4. Tempered stable Lévy motion driven by stable subordinator

    NASA Astrophysics Data System (ADS)

    Gajda, Janusz; Wy?oma?ska, Agnieszka

    2013-08-01

    In this article we propose a new model for financial data description. Combining two independent mechanisms, namely the tempered stable process and inverse stable subordinator, we obtain a new model which captures not only the tempered stable character of the underlying data but also such a property as periods in which the values of an asset stay on the same level. Moreover, we classify our system to the family of subdiffusive processes and investigate its tail behavior. We describe in detail testing and estimation procedures for the proposed model. In the last step we calibrate our model to the real data.

  5. Stable Spheromaks with Profile Control

    SciTech Connect

    Fowler, T K; Jayakumar, R

    2008-01-29

    A spheromak equilibrium with zero edge current is shown to be stable to both ideal MHD and tearing modes that normally produce Taylor relaxation in gun-injected spheromaks. This stable equilibrium differs from the stable Taylor state in that the current density j falls to zero at the wall. Estimates indicate that this current profile could be sustained by non-inductive current drive at acceptable power levels. Stability is determined using the NIMROD code for linear stability analysis. Non-linear NIMROD calculations with non-inductive current drive could point the way to improved fusion reactors.

  6. Earthquakes in Stable Continental Crust.

    ERIC Educational Resources Information Center

    Johnston, Arch C.; Kanter, Lisa R.

    1990-01-01

    Discussed are some of the reasons for earthquakes which occur in stable crust away from familiar zones at the ends of tectonic plates. Crust stability and the reactivation of old faults are described using examples from India and Australia. (CW)

  7. Stable Multibubble Sonoluminescence Bubble Patterns

    SciTech Connect

    Posakony, Gerald J.; Greenwood, Lawrence R.; Ahmed, Salahuddin

    2006-06-30

    Multibubble standing wave patterns can be generated from a flat piezoceramic transducer element propagating into water. By adding a second transducer positioned at 90 degrees from the transducer generating the standing wave, a 3-dimensional volume of stable single bubbles can be established. Further, the addition of the second transducer stabilizes the bubble pattern so that individual bubbles may be studied. The size of the bubbles and the separation of the standing waves depend on the frequency of operation. Two transducers, operating at frequencies above 500 kHz, provided the most graphic results for the configuration used in this study. At these frequencies stable bubbles exhibit a bright sonoluminescence pattern. Whereas stable SBSL is well-known, stable MBSL has not been previously reported. This paper includes discussions of the acoustic responses, standing wave patterns, and pictorial results of the separation of individual bubble of sonoluminescence in a multibubble sonoluminescence environment.

  8. Intramolecular C-H/O-H bond cleavage with water and alcohol using a phosphine-free ruthenium carbene NCN pincer complex.

    PubMed

    Prokopchuk, Demyan E; Tsui, Brian T H; Lough, Alan J; Morris, Robert H

    2014-12-15

    Transition metal complexes that exhibit metal-ligand cooperative reactivity could be suitable candidates for applications in water splitting. Ideally, the ligands around the metal should not contain oxidizable donor atoms, such as phosphines. With this goal in mind, we report new phosphine-free ruthenium NCN pincer complexes with a central N-heterocyclic carbene donor and methylpyridyl N-donors. Reaction with base generates a neutral, dearomatized alkoxo-amido complex, which has been structurally and spectroscopically characterized. The tert-butoxide ligand facilitates regioselective, intramolecular proton transfer through a C?H/O?H bond cleavage process occurring at room temperature. Kinetic and thermodynamic data have been obtained by VT NMR experiments; DFT calculations support the observed behavior. Isolation and structural characterization of a doubly dearomatized phosphine complex also strongly supports our mechanistic proposal. The alkoxo-amido complex reacts with water to form a dearomatized ruthenium hydroxide complex, a first step towards phosphine-free metal-ligand cooperative water splitting. PMID:25266279

  9. Ru(II), Os(II), and Ir(III) complexes with chelating pyridyl-mesoionic carbene ligands: structural characterization and applications in transfer hydrogenation catalysis.

    PubMed

    Bolje, Aljoša; Hohloch, Stephan; van der Meer, Margarethe; Košmrlj, Janez; Sarkar, Biprajit

    2015-04-27

    Chelating ligands with one pyridine donor and one mesoionic carbene donor are fast establishing themselves as privileged ligands in homogeneous catalysis. The synthesis of several new Ir(III)-Cp*- and Os(II)-Cym complexes (Cp* = pentamethylcyclopentadienyl, Cym = p-cymene=4-isopropyl-toluene) derived from chelating pyridyltriazolylidenes where the additional pyridine donor was incorporated via the azide part of the triazole is presented. Furthermore, different 4-substituted phenylacetylene building blocks have been used to introduce electronic fine-tuning in the ligands. The ligands thus can be generally described as 4-(4-R-phenyl)-3-methyl-1-(pyridin-2-yl)-1H-1,2,3-triazol-5-ylidene (with R being H (L(1)), Me (L(2)), OMe (L(3)), CN (L(4)), CF3 (L(5)), Br (L(6)) or NO2 (L(7))). The corresponding complexes (Ir-1 to Ir-7 and Os-1 to Os-7) were characterized by standard spectroscopic methods, and the expected three-legged, piano-stool type coordination was unambiguously confirmed by X-ray diffraction analysis of selected compounds. Together with Ru(II) analogues previously reported by us, a total of 21 complexes were tested as (pre)catalysts for the transfer hydrogenation of carbonyl groups, showing a remarkable reactivity even at very low catalyst loadings. The electronic effects of the ligands as well as different substrates were investigated. Some mechanistic elucidations are also presented. PMID:25752929

  10. Formation of Highly Strained N-Heterocycles via Decomposition of Iron N-Heterocyclic Carbene Complexes: The Value of Labile Fe?C Bonds.

    PubMed

    Haslinger, Stefan; Kück, Jens W; Anneser, Markus R; Cokoja, Mirza; Pöthig, Alexander; Kühn, Fritz E

    2015-12-01

    An unusual, highly-strained annulated 2,2'-biimdazole was isolated as decomposition product of the outer-sphere one-electron oxidation of an iron(II) N-heterocyclic carbene (NHC) complex bearing a tetradentate bis(NHC)-bis- (pyridine) ligand (NCCN). Reductive elimination leading to the 2,2'-biimdazole is a consequence of the lability of the Fe?C bonds in the transient species and also extends to complexes with modified ligands but the same coordination geometry. Closely related by a two-electron redox step to a family of less-strained tetraazafulvalenes, the obtained 2,2'-biimidazolium salts were studied electrochemically. Introduction of methyl substituents at the methylene tether significantly increased the reversibility of the electrochemical reduction. Furthermore, the reactivity of the 2,2'-biimidazolium salt was examined by oxidative addition of [Ni(cod)2 ] to the central C?C bond, providing a previously unknown way for the formation of NHC transition metal complexes. PMID:26486319

  11. Metal Stable Isotopes in Paleoceanography

    NASA Astrophysics Data System (ADS)

    Anbar, Ariel D.; Rouxel, Olivier

    2007-05-01

    Considered esoteric only a few years ago, research into the stable isotope geochemistry of transition metals is moving into the geoscience mainstream. Although initial attention focused on the potential use of some of these nontraditional isotope systems as biosignatures, they are now emerging as powerful paleoceanographic proxies. In particular, the Fe and Mo isotope systems are providing information about changes in oxygenation and metal cycling in ancient oceans. Zn, Cu, Tl, and a number of other metals and metalloids also show promise. Here we review the basis of stable isotope fractionation as it applies to these elements, analytical considerations, and the current status and future prospects of this rapidly developing research area.

  12. Multi-stable cylindrical lattices

    NASA Astrophysics Data System (ADS)

    Pirrera, Alberto; Lachenal, Xavier; Daynes, Stephen; Weaver, Paul M.; Chenchiah, Isaac V.

    2013-11-01

    We present a cylindrical lattice structure that mimics the behaviour of the virus bacteriophage T4 in having two (or more) stable states which differ in their radii and length. While the virus achieves bistability through molecular mechanisms we use composite materials to exploit the interplay between pre-stress, material properties and structural geometry. We demonstrate (computationally) that multi-stability is a robust phenomenon. We also show (analytically) that it is possible to choose the design variables so that the energy is independent of the radius, thus resulting in every state of the structure being stable.

  13. Synthesis and behavior of novel sulfonated water-soluble N-heterocyclic carbene (?(4)-diene) platinum(0) complexes.

    PubMed

    Ruiz-Varilla, Andrea M; Baquero, Edwin A; Silbestri, Gustavo F; Gonzalez-Arellano, Camino; de Jesús, Ernesto; Flores, Juan C

    2015-11-14

    A series of water-soluble (NHC)Pt(0)(dvtms) and (NHC)Pt(0)(AE) complexes containing different sulfonated NHC ligands (dvtms = divinyltetramethyldisiloxane and AE = diallyl ether) are reported. The dvtms compounds have been found to be quite robust and to display some conformational rigidity, whereas their AE counterparts are less stable and more flexible. The catalytic evaluation of these complexes in the hydrosilylation of alkynes in water revealed no benefits in favor of the complexes containing the more labile spectator diene (AE), and a fairly regular catalytic behavior for all complexes that restricts the location of the sulfonate group to the proximity of the metal site. PMID:26346995

  14. Bayesian stable isotope mixing models

    EPA Science Inventory

    In this paper we review recent advances in Stable Isotope Mixing Models (SIMMs) and place them into an over-arching Bayesian statistical framework which allows for several useful extensions. SIMMs are used to quantify the proportional contributions of various sources to a mixtur...

  15. Synthesis of thermally stable polymers

    NASA Technical Reports Server (NTRS)

    Butler, G. B.

    1978-01-01

    The reaction of bis triazo linediones with divinyl esters and substituted styrenes was investigated. Twenty new polymers were derived via reaction of two previously synthesized bis triazol linediones and four new bis atriazol linediones with eight styrenes. The structure and polymer properties of these thermally stable polymers was examined. The reaction of triazo linediones with enol esters was also considered.

  16. LP based approach to optimal stable matchings

    SciTech Connect

    Teo, Chung-Piaw; Sethuraman, J.

    1997-06-01

    We study the classical stable marriage and stable roommates problems using a polyhedral approach. We propose a new LP formulation for the stable roommates problem. This formulation is non-empty if and only if the underlying roommates problem has a stable matching. Furthermore, for certain special weight functions on the edges, we construct a 2-approximation algorithm for the optimal stable roommates problem. Our technique uses a crucial geometry of the fractional solutions in this formulation. For the stable marriage problem, we show that a related geometry allows us to express any fractional solution in the stable marriage polytope as convex combination of stable marriage solutions. This leads to a genuinely simple proof of the integrality of the stable marriage polytope. Based on these ideas, we devise a heuristic to solve the optimal stable roommates problem. The heuristic combines the power of rounding and cutting-plane methods. We present some computational results based on preliminary implementations of this heuristic.

  17. Bis-N-Heterocyclic Carbene Palladium(IV) Tetrachloride Complexes: Synthesis, Reactivity and Mechanisms of Direct Chlorinations and Oxidations of Organic Substrates

    PubMed Central

    McCall, A. Scott; Wang, Hongwang; Desper, John M.; Kraft, Stefan

    2014-01-01

    This paper describes the preparation and isolation of novel octahedral CH2-bridged bis-(N-heterocyclic carbene)palladium(IV) tetrachlorides of the general formula LPdIVCl4 [L = (NHC)CH2(NHC)] from LPdIICl2 and Cl2. In intermolecular, non-chelation controlled transformations LPdIVCl4 reacted with alkenes and alkynes to 1,2-dichlorination adducts. Aromatic, benzylic, and aliphatic CH-bonds were converted into C-Cl bonds. Detailed mechanistic investigations in the dichlorinations of alkenes were conducted on the 18VE PdIV-complex. Positive solvent effects as well as kinetic measurements probing the impact of cyclohexene- and chloride concentrations on the rate of alkene chlorination, support a PdIV-Cl ionization in the first step. Product stereochemistry and product distributions from various alkenes also support Cl+-transfer from the pentacoordinated PdIV-intermediate LPdIVCl3+ to olefins. 1-hexene/3-hexene competition experiments rule out both the formation of ?-complexes along the reaction coordinate as well as in situ generated Cl2 from a reductive elimination process. Instead, a ligand-mediated direct Cl+-transfer from LPdIVCl3+ to the ?-system is likely to occur. Similarly, C-H bond chlorinations proceed via an electrophilic process with in situ formed LPdIVCl3+. The presence of a large excess of added Cl? slows down cyclohexene chlorination while the presence of stoichiometric amounts of chloride accelerates both PdIV-Cl ionization and Cl+-transfer from LPdIVCl3+. 1H NMR titrations, T1 relaxation time measurements, binding isotherms and Job plot analysis point to the formation of a trifurcated Cl?…H-C bond in the NHC-ligand periphery as a supramolecular cause for the accelerated chemical events involving the metal center. PMID:21247150

  18. Luminescent Iridium(III) Complexes Supported by N-Heterocyclic Carbene-based C^C^C-Pincer Ligands and Aromatic Diimines

    PubMed Central

    Chung, Lai-Hon; Lo, Hoi-Shing; Ng, Sze-Wing; Ma, Dik-Lung; Leung, Chung-Hang; Wong, Chun-Yuen

    2015-01-01

    Iridium(III) hydrido complexes containing N-heterocyclic carbene (NHC)-based pincer ligand 1,3-bis(1-butylimidazolin-2-ylidene)phenyl anion (C1^C^C1) or 1,3-bis(3-butylbenzimidazolin-2-ylidene)phenyl anion (C2^C^C2) and aromatic diimine (2,2?-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4?-dimethyl-2,2?-bipyridine (Me2bpy), or dipyrido-[3,2-f:2?,3?-h]-quinoxaline (dpq)) in the form of [Ir(C^C^C)(N^N)(H)]+ have been prepared. Crystal structures for these complexes show that the Ir–CNHC distances are 2.043(5)–2.056(5) Å. The hydride chemical shifts for complexes bearing C1^C^C1 (?20.6 to ?20.3?ppm) are more upfield than those with C2^C^C2 (?19.5 and ?19.2?ppm), revealing that C1^C^C1 is a better electron donor than C2^C^C2. Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations suggest that the lowest-energy electronic transition associated with these complexes (??=?340–530?nm (????103?dm3 mol?1 cm?1)) originate from a d?(IrIII)????*(N^N) metal-to-ligand charge transfer transition, where the d?(IrIII) level contain significant contribution from the C^C^C ligands. All these complexes are emissive in the yellow-spectral region (553–604?nm in CH3CN and CH2Cl2) upon photo-excitation with quantum yields of 10?3–10?1. PMID:26487542

  19. Luminescent Iridium(III) Complexes Supported by N-Heterocyclic Carbene-based C^C^C-Pincer Ligands and Aromatic Diimines

    NASA Astrophysics Data System (ADS)

    Chung, Lai-Hon; Lo, Hoi-Shing; Ng, Sze-Wing; Ma, Dik-Lung; Leung, Chung-Hang; Wong, Chun-Yuen

    2015-10-01

    Iridium(III) hydrido complexes containing N-heterocyclic carbene (NHC)-based pincer ligand 1,3-bis(1-butylimidazolin-2-ylidene)phenyl anion (C1^C^C1) or 1,3-bis(3-butylbenzimidazolin-2-ylidene)phenyl anion (C2^C^C2) and aromatic diimine (2,2?-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4?-dimethyl-2,2?-bipyridine (Me2bpy), or dipyrido-[3,2-f:2?,3?-h]-quinoxaline (dpq)) in the form of [Ir(C^C^C)(N^N)(H)]+ have been prepared. Crystal structures for these complexes show that the Ir–CNHC distances are 2.043(5)–2.056(5) Å. The hydride chemical shifts for complexes bearing C1^C^C1 (?20.6 to ?20.3?ppm) are more upfield than those with C2^C^C2 (?19.5 and ?19.2?ppm), revealing that C1^C^C1 is a better electron donor than C2^C^C2. Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations suggest that the lowest-energy electronic transition associated with these complexes (??=?340–530?nm (????103?dm3 mol?1 cm?1)) originate from a d?(IrIII)????*(N^N) metal-to-ligand charge transfer transition, where the d?(IrIII) level contain significant contribution from the C^C^C ligands. All these complexes are emissive in the yellow-spectral region (553–604?nm in CH3CN and CH2Cl2) upon photo-excitation with quantum yields of 10?3–10?1.

  20. Luminescent Iridium(III) Complexes Supported by N-Heterocyclic Carbene-based C^C^C-Pincer Ligands and Aromatic Diimines.

    PubMed

    Chung, Lai-Hon; Lo, Hoi-Shing; Ng, Sze-Wing; Ma, Dik-Lung; Leung, Chung-Hang; Wong, Chun-Yuen

    2015-01-01

    Iridium(III) hydrido complexes containing N-heterocyclic carbene (NHC)-based pincer ligand 1,3-bis(1-butylimidazolin-2-ylidene)phenyl anion (C(1)^C^C(1)) or 1,3-bis(3-butylbenzimidazolin-2-ylidene)phenyl anion (C(2)^C^C(2)) and aromatic diimine (2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), or dipyrido-[3,2-f:2',3'-h]-quinoxaline (dpq)) in the form of [Ir(C^C^C)(N^N)(H)](+) have been prepared. Crystal structures for these complexes show that the Ir-CNHC distances are 2.043(5)-2.056(5) Å. The hydride chemical shifts for complexes bearing C(1)^C^C(1) (-20.6 to -20.3?ppm) are more upfield than those with C(2)^C^C(2) (-19.5 and -19.2?ppm), revealing that C(1)^C^C(1) is a better electron donor than C(2)^C^C(2). Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations suggest that the lowest-energy electronic transition associated with these complexes (??=?340-530?nm (????10(3)?dm(3) mol(-1) cm(-1))) originate from a d?(Ir(III))????*(N^N) metal-to-ligand charge transfer transition, where the d?(Ir(III)) level contain significant contribution from the C^C^C ligands. All these complexes are emissive in the yellow-spectral region (553-604?nm in CH3CN and CH2Cl2) upon photo-excitation with quantum yields of 10(-3)-10(-1). PMID:26487542

  1. Advanced Thermally Stable Jet Fuels

    SciTech Connect

    A. Boehman; C. Song; H. H. Schobert; M. M. Coleman; P. G. Hatcher; S. Eser

    1998-01-01

    The Penn State program in advanced thermally stable jet fuels has five components: 1) development of mechanisms of degradation and solids formation; 2) quantitative measurement of growth of sub-micrometer and micrometer-sized particles during thermal stressing; 3) characterization of carbonaceous deposits by various instrumental and microscopic methods; 4) elucidation of the role of additives in retarding the formation of carbonaceous solids; and 5) assessment of the potential of producing high yields of cycloalkanes and hydroaromatics from coal.

  2. Stable Skyrmions in Spinor Condensates

    SciTech Connect

    Herbut, Igor F.; Oshikawa, Masaki

    2006-08-25

    Globally symmetric spinor condensates in free space are argued not to support stable topological defects in either two or three dimensions. In the latter case, however, we show that a topological Skyrmion can be stabilized by forcing it to adopt certain density profiles. A sufficient condition for the existence of Skyrmion solutions in three dimensions is formulated and illustrated in simple examples. Our results pertain to Bose-Einstein condensation in {sup 87}Rb.

  3. Shelf-Stable Food Safety

    MedlinePLUS

    ... Administrative Forms Standard Forms Skip Navigation Z7_0Q0619C0JGR010IFST1G5B10H1 Web Content Viewer (JSR 286) Actions ${title} Loading... / Topics / ... Food Safety / Shelf-Stable Food Safety Z7_0Q0619C0JGR010IFST1G5B10H3 Web Content Viewer (JSR 286) Actions ${title} Loading... Z7_ ...

  4. Palladium complexes of abnormal N-heterocyclic carbenes as precatalysts for the much preferred Cu-free and amine-free Sonogashira coupling in air in a mixed-aqueous medium.

    PubMed

    John, Alex; Shaikh, Mobin M; Ghosh, Prasenjit

    2009-12-21

    A series of new PEPPSI (Pyridine Enhanced Precatalyst Preparation Stabilization and Initiation) themed precatalysts of abnormal N-heterocyclic carbenes for the highly desirable Cu-free and amine-free Sonogashira coupling in air in a mixed-aqueous medium is reported. Specifically, the PEPPSI themed (NHC)PdI2(pyridine) type precatalysts, 1b-4b, efficiently carried out the highly convenient Cu-free and amine-free Sonogashira coupling of aryl bromides and iodides with terminal acetylenes in air in a mixed aqueous medium. Complexes, 1b-4b, were synthesized by the direct reaction of the corresponding imidazo[1,2-a]pyridinium iodide salts, 1a-4a, with PdCl2 in pyridine in the presence of K2CO3 as a base while the imidazo[1,2-a]pyridinium iodide salts, 1a-4a, were in turn synthesized by the alkylation reactions of the respective imidazo[1,2-a]pyridine derivatives with alkyl iodides. The density functional theory (DFT) studies revealed that these imidazol-3-ylidene[1,2-a]pyridine derived abnormal carbenes are strongly sigma-donating and consequently significantly weaken the catalytically important labile trans pyridine ligand in 1b-4b. PMID:20023883

  5. Staff detection with stable paths.

    PubMed

    Dos Santos Cardoso, Jaime; Capela, Artur; Rebelo, Ana; Guedes, Carlos; Pinto da Costa, Joaquim

    2009-06-01

    The preservation of musical works produced in the past requires their digitalization and transformation into a machine-readable format. The processing of handwritten musical scores by computers remains far from ideal. One of the fundamental stages to carry out this task is the staff line detection. We investigate a general-purpose, knowledge-free method for the automatic detection of music staff lines based on a stable path approach. Lines affected by curvature, discontinuities, and inclination are robustly detected. Experimental results show that the proposed technique consistently outperforms well-established algorithms. PMID:19372615

  6. Stable reflexive sheaves and localization

    E-print Network

    Gholampour, Amin

    2013-01-01

    We study moduli spaces $\\N$ of rank 2 stable reflexive sheaves on $\\PP^3$. Fixing Chern classes $c_1$, $c_2$, and summing over $c_3$, we consider the generating function $G^{refl}(q)$ of Euler characteristics of such moduli spaces. The action of the dense open torus $T$ on $\\PP^3$ lifts to $\\N$ and we classify all sheaves in $\\N^T$. This leads to an explicit expression for $G^{refl}(q)$. Since $c_3$ is bounded below and above, $G^{refl}(q)$ is a polynomial. For $c_1=-1$, we show its leading term is $12c_2 q^{c_{2}^{2}}$. Next, we study moduli spaces of rank 2 stable torsion free sheaves on $\\PP^3$ and consider the generating function $G(q)$ of Euler characteristics of such moduli spaces. We give an expression for this generating function in terms of $G^{refl}(q)$ and Euler characteristics of Quot schemes of certain $T$-equivariant reflexive sheaves. These Quot schemes and their fixed point loci are studied in a sequel with B. Young. The components of these fixed point loci are products of $\\PP^1$'s and give r...

  7. Stable bound orbits around black rings

    SciTech Connect

    Igata, Takahisa; Ishihara, Hideki; Takamori, Yohsuke

    2010-11-15

    We examine bound orbits of particles around singly rotating black rings. We show that there exist stable bound orbits in toroidal spiral shape near the 'axis' of the ring, and also stable circular orbits on the axis as special cases. The stable bound orbits can have arbitrary large size if the thickness of the ring is less than a critical value.

  8. Uses of stable isotopes in fish ecology

    EPA Science Inventory

    Analyses of fish tissues (other than otoliths) for stable isotope ratios can provide substantial information on fish ecology, including physiological ecology. Stable isotopes of nitrogen and carbon frequently are used to determine the mix of diet sources for consumers. Stable i...

  9. Convergence Rate for Stable Weighted Branching Processes

    E-print Network

    Rösler, Uwe

    ) that Y belongs to the domain of attraction of a stable law of index 1 then Y is said to belong to the domain of normal attraction of an #11;{stable law. In both cases for Y j = Z 1 . It is known that in general Z 1 belongs to the domain of attraction of a stable law of index 1

  10. Stable marriage with general preferences Extended Abstract

    E-print Network

    Könemann, Jochen

    Stable marriage with general preferences Extended Abstract Linda Farczadi, Konstantinos Georgiou of the classical stable marriage problem. In our model, the preferences on one side of the partition are given is practically well-motivated, and as we show, encompasses the well studied hard variant of stable marriage where

  11. Spin-spin contributions to the zero-field splitting tensor in organic triplets, carbenes and biradicals-a density functional and ab initio study.

    PubMed

    Sinnecker, Sebastian; Neese, Frank

    2006-11-01

    An evaluation study for the direct dipolar electron spin-spin (SS) contribution to the zero-field splitting (ZFS) tensor in electron paramagnetic resonance (EPR) spectroscopy is presented. Calculations were performed on a wide variety of organic systems where the SS contribution to the ZFS dominates over the second-order spin-orbit coupling (SOC) contribution. Calculations were performed using (hybrid) density functional theory (DFT), as well as complete active space self-consistent field (CASSCF) wave functions. In the former case, our implementation is an approximation, because we use the two-particle reduced spin-density matrix of the noninteracting reference system. In the latter case, the SS contribution is approximated by a mean-field method which, nevertheless, gives accurate results, compared to the approximation free computation of the SS part in a CASSCF framework. For the case of the triplet dioxygen molecule, it was shown that restricted open-shell density functional theory (RODFT), as well as CASSCF, can provide accurate spin-spin couplings while spin-unrestricted DFT leads to much larger errors. Furthermore, 15 organic radicals, including several 1,3 and 1,5 diradicals, dinitroxide biradicals, and even a chlorophyll a model system, were examined as test cases to demonstrate the accuracy and efficiency of our approach within a DFT framework. Accurate D values with root-mean-square deviations of 0.0035 cm(-1) were obtained. Furthermore, all trends, including those due to substituent effects, were correctly reproduced. In a different set of calculations, the polyacenes benzene, naphthalene, anthracene, and tetracene were studied. Applying DFT, the absolute D values were noticeably underestimated, but it was possible to correctly reproduce the trend to smaller D values with larger size of the systems. Finally, it was demonstrated that our approach is also well-suited for the study of carbenes. The smaller organic radicals of this work were also studied, through the use of CASSCF wave functions. This was a special advantage in the case of the triplet polyacenes, where the CASSCF approach gave better results than the DFT method. In comparing spin-restricted and spin-unrestricted results, it was shown through a natural orbital analysis and comparison to high-level ab initio calculations that even small amounts of spin polarization introduced by the unrestricted calculations lead to large deviations between the unrestricted Kohn-Sham (UKS) and restricted open-shell Kohn-Sham (ROKS) approaches. It is challenging to understand why the ROKS results show much better correlation with the experimental data. PMID:17078624

  12. Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Reactivity in Selected Olefin Metathesis Reactions and Immobilization on Silica.

    PubMed

    Sen, Suman; Schowner, Roman; Imbrich, Dominik A; Frey, Wolfgang; Hunger, Michael; Buchmeiser, Michael R

    2015-09-21

    The synthesis and single-crystal X-ray structures of the novel molybdenum imido alkylidene N-heterocyclic carbene complexes [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf)2] (3), [Mo(N-2,6-Me2C6H3)(IMes)(CHCMe2Ph)(OTf)2] (4), [Mo(N-2,6-Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf){OCH(CF3)2}] (5), [Mo(N-2,6-Me2C6H3)(CH3CN)(IMesH2)(CHCMe2Ph)(OTf)](+)BArF(-) (6), [Mo(N-2,6-Cl2C6H3)(IMesH2)(CHCMe3)(OTf)2] (7) and [Mo(N-2,6-Cl2C6H3)(IMes)(CHCMe3)(OTf)2] (8) are reported (IMesH2=1,3-dimesitylimidazolidin-2-ylidene, IMes=1,3-dimesitylimidazolin-2-ylidene, BArF(-)=tetrakis-[3,5-bis(trifluoromethyl)phenyl] borate, OTf=CF3SO3(-)). Also, silica-immobilized versions I1 and I2 were prepared. Catalysts 3-8, I1 and I2 were used in homo-, cross-, and ring-closing metathesis (RCM) reactions and in the cyclopolymerization of ?,?-diynes. In the RCM of ?,?-dienes, in the homometathesis of 1-alkenes, and in the ethenolysis of cyclooctene, turnover numbers (TONs) up to 100,000, 210,000 and 30,000, respectively, were achieved. With I1 and I2, virtually Mo-free products were obtained (<3?ppm Mo). With 1,6-hepta- and 1,7-octadiynes, catalysts 3, 4, and 5 allowed for the regioselective cyclopolymerization of 4,4-bis(ethoxycarbonyl)-1,6-heptadiyne, 4,4-bis(hydroxymethyl)-1,6-heptadiyne, 4,4-bis[(3,5-diethoxybenzoyloxy)methyl]-1,6-heptadiyne, 4,4,5,5-tetrakis(ethoxycarbonyl)-1,7-octadiyne, and 1,6-heptadiyne-4-carboxylic acid, underlining the high functional-group tolerance of these novel Group?6 metal alkylidenes. PMID:26249141

  13. Stable density stratification solar pond

    NASA Technical Reports Server (NTRS)

    Lansing, F. L. (inventor)

    1985-01-01

    A stable density-stratification solar pond for use in the collection and storage of solar thermal energy including a container having a first section characterized by an internal wall of a substantially cylindrical configuration and a second section having an internal wall of a substantially truncated conical configuration surmounting the first section in coaxial alignment therewith, the second section of said container being characterized by a base of a diameter substantially equal to the diameter of the first section and a truncated apex defining a solar energy acceptance opening is discussed. A body of immiscible liquids is disposed within the container and comprises a lower portion substantially filling the first section of the container and an upper portion substantially filling the second section of the container, said lower portion being an aqueous based liquid of a darker color than the upper portion and of a greater density. A protective cover plate is removably provided for covering the acceptance opening.

  14. Stable States of Biological Organisms

    E-print Network

    Yukalov, V I; Yukalova, E P; Henry, J -Y; Cobb, J P

    2009-01-01

    A novel model of biological organisms is advanced, treating an organism as a self-consistent system subject to a pathogen flux. The principal novelty of the model is that it describes not some parts, but a biological organism as a whole. The organism is modeled by a five-dimensional dynamical system. The organism homeostasis is described by the evolution equations for five interacting components: healthy cells, ill cells, innate immune cells, specific immune cells, and pathogens. The stability analysis demonstrates that, in a wide domain of the parameter space, the system exhibits robust structural stability. There always exist four stable stationary solutions characterizing four qualitatively differing states of the organism: alive state, boundary state, critical state, and dead state.

  15. Labeling Monosaccharides With Stable Isotopes.

    PubMed

    Zhang, Wenhui; Zhao, Shikai; Serianni, Anthony S

    2015-01-01

    Chemical and chemi-enzymic methods are discussed for the preparation of monosaccharide isotopomers that are singly and multiply labeled with (13)C, (2)H, (17/18)O, and (15)N isotopes. The discussion focuses primarily on chemical methods to incorporate stable isotopes into monosaccharides and not on methods to assemble labeled monosaccharides into more complex biomolecules such as oligosaccharides or oligonucleotides. Two primary isotope insertion reactions are considered: cyanohydrin reduction (CR) and molybdate-catalyzed epimerization (MCE). Both methods are described in detail, including discussions of their mechanistic features, and their advantages and limitations. The integration of CR, MCE, and other chemical synthetic processes with enzyme-mediated synthesis is also discussed to illustrate how a wide range of singly and multiply labeled monosaccharides can be prepared for subsequent use in the assembly of more complex isotopically labeled biomolecules. PMID:26577741

  16. Dimensionally stable metallic hydride composition

    DOEpatents

    Heung, Leung K. (Aiken, SC)

    1994-01-01

    A stable, metallic hydride composition and a process for making such a composition. The composition comprises a uniformly blended mixture of a metal hydride, kieselguhr, and a ballast metal, all in the form of particles. The composition is made by subjecting a metal hydride to one or more hydrogen absorption/desorption cycles to disintegrate the hydride particles to less than approximately 100 microns in size. The particles are partly oxidized, then blended with the ballast metal and the kieselguhr to form a uniform mixture. The mixture is compressed into pellets and calcined. Preferably, the mixture includes approximately 10 vol. % or more kieselguhr and approximately 50 vol. % or more ballast. Metal hydrides that can be used in the composition include Zr, Ti, V, Nb, Pd, as well as binary, tertiary, and more complex alloys of La, Al, Cu, Ti, Co, Ni, Fe, Zr, Mg, Ca, Mn, and mixtures and other combinations thereof. Ballast metals include Al, Cu and Ni.

  17. Stable massive particles at colliders

    SciTech Connect

    Fairbairn, M.; Kraan, A.C.; Milstead, D.A.; Sjostrand, T.; Skands, P.; Sloan, T.; ,

    2006-11-01

    We review the theoretical motivations and experimental status of searches for stable massive particles (SMPs) which could be sufficiently long-lived as to be directly detected at collider experiments. The discovery of such particles would address a number of important questions in modern physics including the origin and composition of dark matter in the universe and the unification of the fundamental forces. This review describes the techniques used in SMP-searches at collider experiments and the limits so far obtained on the production of SMPs which possess various colour, electric and magnetic charge quantum numbers. We also describe theoretical scenarios which predict SMPs, the phenomenology needed to model their production at colliders and interactions with matter. In addition, the interplay between collider searches and open questions in cosmology such as dark matter composition are addressed.

  18. Stable reflexive sheaves and localization

    E-print Network

    Amin Gholampour; Martijn Kool

    2015-09-14

    We study moduli spaces $\\mathcal{N}$ of rank 2 stable reflexive sheaves on $\\mathbb{P}^3$. Fixing Chern classes $c_1$, $c_2$, and summing over $c_3$, we consider the generating function $\\mathsf{Z}^{\\mathrm{refl}}(q)$ of Euler characteristics of such moduli spaces. The action of the dense open torus $T$ on $\\mathbb{P}^3$ lifts to $\\mathcal{N}$ and we classify all sheaves in $\\mathcal{N}^T$. This leads to an explicit expression for $\\mathsf{Z}^{\\mathrm{refl}}(q)$. Since $c_3$ is bounded below and above, $\\mathsf{Z}^{\\mathrm{refl}}(q)$ is a polynomial. For $c_1=-1$, we show its leading term is $12c_2 q^{c_{2}^{2}}$. Next, we study moduli spaces of rank 2 stable torsion free sheaves on $\\mathbb{P}^3$ and consider the generating function $\\mathsf{Z}(q)$ of Euler characteristics of such moduli spaces. We give an expression for this generating function in terms of $\\mathsf{Z}^{\\mathrm{refl}}(q)$ and Euler characteristics of Quot schemes of certain $T$-equivariant reflexive sheaves. These Quot schemes and their fixed point loci are studied in a sequel with B. Young. The components of these fixed point loci are products of $\\mathbb{P}^1$'s and give rise non-trivial combinatorics. For $c_1=-1$ and $c_2=1$, we obtain $\\mathsf{Z}(q) = 4(q+q^{-1}) M(q^{-2})^8$, where $M(q)$ is the MacMahon function. Many techniques of this paper apply to any toric 3-fold. In general, $\\mathsf{Z}^{\\mathrm{refl}}(q)$ depends on the choice of polarization which leads to wall-crossing phenomena. We briefly illustrate this in the case of $\\mathbb{P}^2 \\times \\mathbb{P}^1$.

  19. Stable line defects in silicene

    NASA Astrophysics Data System (ADS)

    Ghosh, Dibyajyoti; Parida, Prakash; Pati, Swapan K.

    2015-11-01

    Line defects in two-dimensional (2D) materials greatly modulate various properties of their pristine form. Using ab initio molecular dynamics (AIMD) simulations, we investigate the structural reconstructions of different kinds of grain boundaries in the silicene sheets. It is evident that depending upon the presence of silicon adatoms and edge shape of grain boundaries (i.e., armchair or zigzag), stable extended line defects (ELDs) can be introduced in a controlled way. Further studies show the stability of these line-defects in silicene, grown on Ag(111) surface at room-temperature. Importantly, unlike most of the 2D sheet materials such as graphene and hexagonal boron nitride, 5-5-8 line defects modify the nonmagnetic semimetallic pristine silicene sheet to spin-polarized metal. As ferromagnetically ordered magnetic moments remain strongly localized at the line defect, a one-dimensional spin channel gets created in silicene. Interestingly, these spin channels are quite stable because, unlike the edge of nanoribbons, structural reconstruction or contamination cannot destroy the ordering of magnetic moments here. Zigzag silicene nanoribbons with a 5-5-8 line defect also exhibit various interesting electronic and magnetic properties depending upon their width as well as the nature of the magnetic coupling between edge and defect spin states. Upon incorporation of other ELDs, such as 4-4-4 and 4-8 defects, 2D sheets and nanoribbons of silicene show a nonmagnetic metallic or semiconducting ground state. Highlighting the controlled formation of ELDs and consequent emergence of technologically important properties in silicene, we propose new routes to realize silicene-based nanoelectronic and spintronic devices.

  20. On Nonstable and Stable Population Momentum

    PubMed Central

    Olgiati, Analia S.; Levin, Simon A.

    2014-01-01

    This article decomposes total population momentum into two constituent and multiplicative parts: “nonstable” momentum and “stable” momentum. Nonstable momentum depends on deviations between a population’s current age distribution and its implied stable age distribution. Stable momentum is a function of deviations between a population’s implied stable and stationary age distributions. In general, the factorization of total momentum into the product of nonstable and stable momentum is a very good approximation. The factorization is exact, however, when the current age distribution is stable or when observed fertility is already at replacement. We provide numerical illustrations by calculating nonstable, stable, and total momentum for 176 countries, the world, and its major regions. In short, the article brings together disparate strands of the population momentum literature and shows how the various kinds of momentum fit together into a single unifying framework. PMID:21948106

  1. Hydrogen-bonding pincer complexes with two protic N-heterocyclic carbenes from direct metalation of a 1,8-bis(imidazol-1-yl)carbazole by platinum, palladium, and nickel.

    PubMed

    Marelius, David C; Darrow, Evan H; Moore, Curtis E; Golen, James A; Rheingold, Arnold L; Grotjahn, Douglas B

    2015-07-27

    Pincer protic N-heterocyclic carbene (PNHC) complexes were synthesized by direct metalation, the formation of a metal carbon bond from an unfunctionalized C?H bond in a single synthetic step. Significantly, direct metalation succeeded even for a first-row metal, nickel. The chloride complexes were isolated and then converted to the acetate, triflate, or in the platinum case, a hydride analogue. Crystal structures and (1) H, (13) C, and (15) N?NMR data, as well as IR spectra, document the effects of intramolecular hydrogen bonding and the planar but flexible pincer framework. Anti-Markovnikov addition of O?H bonds to alkynes, including catalyzed alkyne hydration, were demonstrated on the Pt triflate analog. PMID:26134355

  2. Concerted Amidation of Activated Esters: Reaction Path and Origins of Selectivity in the Kinetic Resolution of Cyclic Amines via N-Heterocyclic Carbenes and Hydroxamic Acid Cocatalyzed Acyl Transfer

    PubMed Central

    2015-01-01

    The N-heterocyclic carbene and hydroxamic acid cocatalyzed kinetic resolution of cyclic amines generates enantioenriched amines and amides with selectivity factors up to 127. In this report, a quantum mechanical study of the reaction mechanism indicates that the selectivity-determining aminolysis step occurs via a novel concerted pathway in which the hydroxamic acid plays a key role in directing proton transfer from the incoming amine. This modality was found to be general in amide bond formation from a number of activated esters including those generated from HOBt and HOAt, reagents that are broadly used in peptide coupling. For the kinetic resolution, the proposed model accurately predicts the faster reacting enantiomer. A breakdown of the steric and electronic control elements shows that a gearing effect in the transition state is responsible for the observed selectivity. PMID:25050843

  3. Magnetic properties of 1 : 4 complexes of CoCl2 and pyridines carrying carbenes (S(0) = 4/2, 6/2, and 8/2) in diluted frozen solution; influence of carbene multiplicity on heterospin single-molecule magnets.

    PubMed

    Karasawa, Satoru; Nakano, Kimihiro; Tanokashira, Jun-ichi; Yamamoto, Noriko; Yoshizaki, Takahito; Koga, Noboru

    2012-11-28

    The microcrystalline sample of a parent complex, [CoCl(2)(py)(4)], showed a single-molecule magnet (SMM) behavior with an effective activation barrier, U(eff)/k(B), of 16 K for reversal of the magnetism in the presence of a dc field of 3 kOe. Pyridine ligands having 2-4 diazo moieties, DYpy; Y = 2, 3l, 3b, and 4, were prepared and confirmed to be quintet, septet, septet, and nonet in the ground state, respectively, after irradiation. The 1 : 4 complexes, CoCl(2)(DYpy)(4); Y = 2, 3l, 3b, and 4 in frozen solutions after irradiation showed the magnetic behaviors of SMMs with total spin multiplicity, S(total) = 17/2, 25/2, 25/2, and 33/2, respectively. Hysteresis loops depending on the temperature were observed and the values of coercive force, H(c), at 1.9 K were 12, 8.4, 11, and 8.1 kOe for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively. In dynamic magnetic susceptibility experiments, ac magnetic susceptibility data obeyed the Arrhenius law to give U(eff)/k(B) values of 94, 92, 93, and 87 K for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively, while the relaxation times for CoCl(2)(CYpy)(4); Y = 2 and 3l, obtained by dc magnetization decay in the range of 3.5-1.9 K slightly deviated downward from Arrhenius plots on cooling. The dynamic magnetic behaviors for CoCl(2)(CYpy)(4) including [CoCl(2)(py)(4)] and CoCl(2)(C1py)(4) suggested that the generated carbenes interacted with the cobalt ion to increase the relaxation time, ?(q), due to the spin quantum tunneling magnetization, which became larger with increasing S(total) of the complex. PMID:22898723

  4. Formation of stable clusters in colloidal suspensions.

    PubMed

    Kovalchuk, Nina; Starov, Victor; Langston, Paul; Hilal, Nidal

    2009-01-01

    The experimental evidence and theoretical explanations of stable cluster formation in colloidal suspensions are reviewed. The clusters form in the intermediate range between a stable suspension built up by singlets and the irreversible coagulation or gelation of the suspension. The stable clusters develop as a result of a balance between competing short range attraction and long range repulsion between colloidal particles or due to reversible flocculation in the shallow secondary potential well. Heteroaggregation in binary colloids can also result in formation of stable clusters. PMID:19073333

  5. Advanced thermally stable jet fuels

    SciTech Connect

    Schobert, H.H.

    1999-01-31

    The Pennsylvania State University program in advanced thermally stable coal-based jet fuels has five broad objectives: (1) Development of mechanisms of degradation and solids formation; (2) Quantitative measurement of growth of sub-micrometer and micrometer-sized particles suspended in fuels during thermal stressing; (3) Characterization of carbonaceous deposits by various instrumental and microscopic methods; (4) Elucidation of the role of additives in retarding the formation of carbonaceous solids; (5) Assessment of the potential of production of high yields of cycloalkanes by direct liquefaction of coal. Future high-Mach aircraft will place severe thermal demands on jet fuels, requiring the development of novel, hybrid fuel mixtures capable of withstanding temperatures in the range of 400--500 C. In the new aircraft, jet fuel will serve as both an energy source and a heat sink for cooling the airframe, engine, and system components. The ultimate development of such advanced fuels requires a thorough understanding of the thermal decomposition behavior of jet fuels under supercritical conditions. Considering that jet fuels consist of hundreds of compounds, this task must begin with a study of the thermal degradation behavior of select model compounds under supercritical conditions. The research performed by The Pennsylvania State University was focused on five major tasks that reflect the objectives stated above: Task 1: Investigation of the Quantitative Degradation of Fuels; Task 2: Investigation of Incipient Deposition; Task 3: Characterization of Solid Gums, Sediments, and Carbonaceous Deposits; Task 4: Coal-Based Fuel Stabilization Studies; and Task 5: Exploratory Studies on the Direct Conversion of Coal to High Quality Jet Fuels. The major findings of each of these tasks are presented in this executive summary. A description of the sub-tasks performed under each of these tasks and the findings of those studies are provided in the remainder of this volume (Sections 1 through 5).

  6. Blood feeding behavior of the stable fly

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stable fly is a fly that looks similar to a house fly but both sexes are blood feeders. Blood is required for successful fertilization and development of eggs. Bites are painful but there is usually no pain after the fly stops feeding. The stable fly is a persistent feeder and will continue trying t...

  7. Bi-stable optical element actuator device

    DOEpatents

    Holdener, Fred R. (Tracy, CA); Boyd, Robert D. (Livermore, CA)

    2002-01-01

    The present invention is a bistable optical element actuator device utilizing a powered means to move an actuation arm, to which an optical element is attached, between two stable positions. A non-powered means holds the actuation arm in either of the two stable positions. The optical element may be a electromagnetic (EM) radiation or particle source, an instrument, or EM radiation or particle transmissive reflective or absorptive elements. A bearing is used to transfer motion and smoothly transition the actuation arm between the two stable positions.

  8. Applications of stable isotopes in clinical pharmacology

    PubMed Central

    Schellekens, Reinout C A; Stellaard, Frans; Woerdenbag, Herman J; Frijlink, Henderik W; Kosterink, Jos G W

    2011-01-01

    This review aims to present an overview of the application of stable isotope technology in clinical pharmacology. Three main categories of stable isotope technology can be distinguished in clinical pharmacology. Firstly, it is applied in the assessment of drug pharmacology to determine the pharmacokinetic profile or mode of action of a drug substance. Secondly, stable isotopes may be used for the assessment of drug products or drug delivery systems by determination of parameters such as the bioavailability or the release profile. Thirdly, patients may be assessed in relation to patient-specific drug treatment; this concept is often called personalized medicine. In this article, the application of stable isotope technology in the aforementioned three areas is reviewed, with emphasis on developments over the past 25 years. The applications are illustrated with examples from clinical studies in humans. PMID:21801197

  9. Semiconductor Nanowires Stable Isotopes in the Amazon

    E-print Network

    Are quakes connected? Semiconductor Nanowires Stable Isotopes in the Amazon Shock-induced Chemistry in the Amazon The upcoming technology revolution in computing, energy, medicine, and virtually everything else

  10. Backtracking Membrane Systems Unravel Stable Oscillations in

    E-print Network

    Hinze, Thomas

    Backtracking Membrane Systems Unravel Stable Oscillations in Distributed Reaction Networks Thomas of membrane systems [11] towards an underly- ing backtracking mechanism able to explore the nature example: membrane division membrane merge complex decomposition molecular transport formation complex

  11. DNA modifications: Another stable base in DNA

    NASA Astrophysics Data System (ADS)

    Brazauskas, Pijus; Kriaucionis, Skirmantas

    2014-12-01

    Oxidation of 5-methylcytosine has been proposed to mediate active and passive DNA demethylation. Tracking the history of DNA modifications has now provided the first solid evidence that 5-hydroxymethylcytosine is a stable epigenetic modification.

  12. Stable Isotope Signatures for Microbial Forensics

    SciTech Connect

    Kreuzer, Helen W.

    2012-01-03

    The isotopic distribution of the atoms composing the molecules of microorganisms is a function of the substrates used by the organisms. The stable isotope content of an organism is fixed so long as no further substrate consumption and biosynthesis occurs, while the radioactive isotopic content decays over time. The distribution of stable isotopes of C, N, O and H in heterotrophic microorganisms is a direct function of the culture medium, and therefore the stable isotope composition can be used to associate samples with potential culture media and also with one another. The 14C content depends upon the 14C content, and therefore the age, of the organic components of the culture medium, as well as on the age of the culture itself. Stable isotope signatures can thus be used for sample matching, to associate cultures with specific growth media, and to predict characteristics of growth media.

  13. An unsupported transition metal-lanthanide bond; synthesis and crystal structure of an Nd-Fe amido N-heterocyclic carbene complex 

    E-print Network

    Arnold, Polly; McMaster, J.; Liddle, S.T.

    2009-01-01

    A salt-elimination reaction between the neodymium monoiodide [Nd(L)(N)(I)]2 [L = ButNCH2CH2{C(NCSiMe3CHNBut)}; N = N(SiMe3)2] and K[FeCp(CO)2] affords the first complex with an unsupported 4f–3d metal–metal bond that is sufficiently stable...

  14. Suppression of Stable Flies on Cattle 

    E-print Network

    Tomberlin, Jeffery K.

    2004-07-01

    can develop each year. The eggs are typically laid in wet straw, such as around hay bales (Fig. 3) or in other decomposing vegetation mixed with the urine and feces produced by the confined animals. Management To suppress stable fly populations... animal facilities, a top priority should be to eliminate stable fly breeding sites as often as possible. To do this, remove and spread decomposing vegetation or bedding material that has become mixed with urine and feces. Doing so will allow the material...

  15. Moving Stable Solitons in Galileon Theory

    E-print Network

    Ali Masoumi; Xiao Xiao

    2012-07-17

    Despite the no-go theorem [5] which rules out static stable solitons in Galileon theory, we propose a family of solitons that evade the theorem by traveling at the speed of light. These domain-wall-like solitons are stable under small fluctuations-analysis of perturbation shows neither ghost-like nor tachyon-like instabilities, and perturbative collision of these solitons suggests that they pass through each other asymptotically, which maybe an indication of the integrability of the theory itself.

  16. A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp(3)?, ?, and ? carbon-fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes.

    PubMed

    Yuan, Jian; Hughes, Russell P; Rheingold, Arnold L

    2015-12-01

    The (pentafluoroethyl)(trifluoromethyl)carbene complex Cp*Ir(CO)[[double bond, length as m-dash]C(CF3)(C2F5)] was synthesized by the reductive activation of the ?-C-F bond in the perfluoro-sec-butyl-iridium complex Cp*Ir(CO)[CF(CF3)(C2F5)](I) with Na/Pb alloy. This compound exists as two geometric isomers in solution; the structure of one isomer has been determined by a single crystal X-ray diffraction study and contains two independent molecules in the asymmetric unit. Further reduction of this carbene complex with Na/Pb alloy afforded the perfluoro-2-butyne iridium complex Cp*Ir(CO)(?(2)-CF3C[triple bond, length as m-dash]CCF3) by an overall 2-electron reduction and elimination of two ?-fluorides. When magnesium graphite was utilized as the reducing agent for the further reduction, Cp*Ir(CO)(?(2)-CF3C[triple bond, length as m-dash]CCF3) was produced as a minor product and the major product was the perfluoroiridacyclobutene complex Cp*Ir(CO)(?(2,4)-CF3CCFCF2) resulting from a ?-C-F bond activation. Direct reduction of the precursor Cp*Ir(CO)[CF(CF3)(C2F5)](i) with magnesium graphite generated the tetrafluorobutatriene iridium complex Cp*Ir(CO)(?(2,3)-CF2[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CF2) along with the perfluoro-2-butyne complex and perfluoroiridacyclobutene complexes in a ratio of 1?:?2?:?6. These reductive inner-sphere pathways to unsaturated fluorocarbon ligands illustrate that carbon-fluorine bond activation can take place at ?-, ?- and ?-carbons but that selectivity in these heterogeneous reductions is difficult to control, with a variety of fluoride eliminations possible for complex perfluoroalkyl ligands. Density Functional Theory (DFT/B3LYP-D3/LACV3P**++) is used to explore the relative energetics of products and intermediates in these reactions. PMID:26158776

  17. Concentration of stable elements in food products

    SciTech Connect

    Montford, M.A.; Shank, K.E.; Hendricks, C.; Oakes, T.W.

    1980-01-01

    Food samples were taken from commercial markets and analyzed for stable element content. The concentrations of most stable elements (Ag, Al, As, Au, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hf, I, K, La, Mg, Mn, Mo, Na, Rb, Sb, Sc, Se, Sr, Ta, Th, Ti, V, Zn, Zr) were determined using multiple-element neutron activation analysis, while the concentrations of other elements (Cd, Hg, Ni, Pb) were determined using atomic absorption. The relevance of the concentrations found are noted in relation to other literature values. An earlier study was extended to include the determination of the concentration of stable elements in home-grown products in the vicinity of the Oak Ridge National Laboratory. Comparisons between the commercial and local food-stuff values are discussed.

  18. Low work function, stable thin films

    DOEpatents

    Dinh, Long N. (Concord, CA); McLean, II, William (Oakland, CA); Balooch, Mehdi (Berkeley, CA); Fehring, Jr., Edward J. (Dublin, CA); Schildbach, Marcus A. (Livermore, CA)

    2000-01-01

    Generation of low work function, stable compound thin films by laser ablation. Compound thin films with low work function can be synthesized by simultaneously laser ablating silicon, for example, and thermal evaporating an alkali metal into an oxygen environment. For example, the compound thin film may be composed of Si/Cs/O. The work functions of the thin films can be varied by changing the silicon/alkali metal/oxygen ratio. Low work functions of the compound thin films deposited on silicon substrates were confirmed by ultraviolet photoelectron spectroscopy (UPS). The compound thin films are stable up to 500.degree. C. as measured by x-ray photoelectron spectroscopy (XPS). Tests have established that for certain chemical compositions and annealing temperatures of the compound thin films, negative electron affinity (NEA) was detected. The low work function, stable compound thin films can be utilized in solar cells, field emission flat panel displays, electron guns, and cold cathode electron guns.

  19. High-Order Energy Stable WENO Schemes

    NASA Technical Reports Server (NTRS)

    Yamaleev, Nail K.; Carpenter, Mark H.

    2008-01-01

    A new third-order Energy Stable Weighted Essentially NonOscillatory (ESWENO) finite difference scheme for scalar and vector linear hyperbolic equations with piecewise continuous initial conditions is developed. The new scheme is proven to be stable in the energy norm for both continuous and discontinuous solutions. In contrast to the existing high-resolution shock-capturing schemes, no assumption that the reconstruction should be total variation bounded (TVB) is explicitly required to prove stability of the new scheme. A rigorous truncation error analysis is presented showing that the accuracy of the 3rd-order ESWENO scheme is drastically improved if the tuning parameters of the weight functions satisfy certain criteria. Numerical results show that the new ESWENO scheme is stable and significantly outperforms the conventional third-order WENO finite difference scheme of Jiang and Shu in terms of accuracy, while providing essentially nonoscillatory solutions near strong discontinuities.

  20. High-Order Energy Stable WENO Schemes

    NASA Technical Reports Server (NTRS)

    Yamaleev, Nail K.; Carpenter, Mark H.

    2009-01-01

    A third-order Energy Stable Weighted Essentially Non-Oscillatory (ESWENO) finite difference scheme developed by Yamaleev and Carpenter was proven to be stable in the energy norm for both continuous and discontinuous solutions of systems of linear hyperbolic equations. Herein, a systematic approach is presented that enables 'energy stable' modifications for existing WENO schemes of any order. The technique is demonstrated by developing a one-parameter family of fifth-order upwind-biased ESWENO schemes; ESWENO schemes up to eighth order are presented in the appendix. New weight functions are also developed that provide (1) formal consistency, (2) much faster convergence for smooth solutions with an arbitrary number of vanishing derivatives, and (3) improved resolution near strong discontinuities.

  1. Stable high-temperature (500 °C) thermistors

    NASA Astrophysics Data System (ADS)

    Carlson, R. O.

    1984-12-01

    Thermistors which are stable in their resistance-temperature characteristic after extended high-temperature exposure have been formed by attaching platinum wires or Fernico (Kovar) ribbons with Birox thick film paste to thermistor spinel material (from two vendors) with a resistivity of 2000 ? cm. Other resistivity compositions were not stable at elevated temperatures. Shifts in the original calibration curve were less than 2 °C at room temperature after 10 000 h at 240 °C, even with periodic jumps to 500 °C. Held and measured at 500 °C, resistance shifts were less than 2 °C for periods up to 750 h. These thermistor structures should provide low-cost, stable, reliable, and interchangeable temperature sensors for oven and furnace measurement and control.

  2. Stable Isotope Enrichment Capabilities at ORNL

    SciTech Connect

    Egle, Brian; Aaron, W Scott; Hart, Kevin J

    2013-01-01

    The Oak Ridge National Laboratory (ORNL) and the US Department of Energy Nuclear Physics Program have built a high-resolution Electromagnetic Isotope Separator (EMIS) as a prototype for reestablishing a US based enrichment capability for stable isotopes. ORNL has over 60 years of experience providing enriched stable isotopes and related technical services to the international accelerator target community, as well as medical, research, industrial, national security, and other communities. ORNL is investigating the combined use of electromagnetic and gas centrifuge isotope separation technologies to provide research quantities (milligram to several kilograms) of enriched stable isotopes. In preparation for implementing a larger scale production facility, a 10 mA high-resolution EMIS prototype has been built and tested. Initial testing of the device has simultaneously collected greater than 98% enriched samples of all the molybdenum isotopes from natural abundance feedstock.

  3. Stable Tricyclic Antitubercular Ozonides Derived from Artemisinin.

    PubMed

    Chaudhary, Sandeep; Sharma, Vashundhra; Jaiswal, Pradeep K; Gaikwad, Anil N; Sinha, Sudhir K; Puri, Sunil K; Sharon, Ashoke; Maulik, Prakas R; Chaturvedi, Vinita

    2015-10-16

    New, highly stable tricyclic antitubercular ozonides 9 and 10 derived from artemisinin are reported in 39 and 9% yields, respectively. The ozonide groups of 9 and 10 were found to be stable under strong basic and acidic conditions. The absolute configuration of ozonides 9 was confirmed by X-ray crystallography. Ozonide 10 shows promising antitubercular activity against M. tuberculosis H37Ra and M. tuberculosis H37Rv with MIC values of 0.39 and 3.12 ?g/mL, respectively. PMID:26430796

  4. Contribution of stable sources to ICRF improvements

    NASA Astrophysics Data System (ADS)

    Gontier, A.-M.; Feissel-Vernier, Martine

    2005-01-01

    A set of stable compact radio sources is proposed for the future maintenance of the ICRF axes using VLBI-derived time series of coordinates of extragalactic radio sources. The proposed selection scheme makes a combined use of statistical and deterministic tests. It identifies 199 stable sources to be compared to the current 212 defining sources. Their consideration for the maintenance of the frame axes is expected to improve the frame stability by a factor of five reaching the level of less than 10 microarcseconds in the medium term. The time behaviour of the radio source directions and their type of noise will be presented.

  5. Using consistent subcuts for detecting stable properties

    NASA Technical Reports Server (NTRS)

    Marzullo, Keith; Sabel, Laura

    1992-01-01

    We present a general protocol for detecting whether a property holds in a distributed system, where the property is a member of a subclass of stable properties we call the locally stable properties. Our protocol is based on a decentralized method for constructing a maximal subset of the local states that are mutually consistent, which in turn is based on a weakened version of vectored time stamps. The structure of our protocol lends itself to refinement, and we demonstrate its utility by deriving some specialized property-detection protocols, including two previously known protocols that are known to be effective.

  6. Development of thermally stable polymer concrete

    SciTech Connect

    Megahed, T.N.E.D., Kukacka, L.E.; Fontana, J.J.

    1989-10-01

    This work pertains to the development of a polymer concrete type that is thermally stable under working temperatures of 200{degree} to 300{degree}F. This material is highly durable and thermally stable with high flexural strength and ductility. Its consistency, while fresh, is suitable for both casting in place or precasting techniques. Several optimization stages were applied ranging from mixing ratios and type of aggregate to resin formulation itself. An optimized range of mixing ratios is developed along with optimized mix ingredients, relating mechanical performance to elevated temperature at various degrees of workability.

  7. Stable isotopes in Lithuanian bioarcheological material

    NASA Astrophysics Data System (ADS)

    Skipityte, Raminta; Jankauskas, Rimantas; Remeikis, Vidmantas

    2015-04-01

    Investigation of bioarcheological material of ancient human populations allows us to understand the subsistence behavior associated with various adaptations to the environment. Feeding habits are essential to the survival and growth of ancient populations. Stable isotope analysis is accepted tool in paleodiet (Schutkowski et al, 1999) and paleoenvironmental (Zernitskaya et al, 2014) studies. However, stable isotopes can be useful not only in investigating human feeding habits but also in describing social and cultural structure of the past populations (Le Huray and Schutkowski, 2005). Only few stable isotope investigations have been performed before in Lithuanian region suggesting a quite uniform diet between males and females and protein intake from freshwater fish and animal protein. Previously, stable isotope analysis has only been used to study a Stone Age population however, more recently studies have been conducted on Iron Age and Late medieval samples (Jacobs et al, 2009). Anyway, there was a need for more precise examination. Stable isotope analysis were performed on human bone collagen and apatite samples in this study. Data represented various ages (from 5-7th cent. to 18th cent.). Stable carbon and nitrogen isotope analysis on medieval populations indicated that individuals in studied sites in Lithuania were almost exclusively consuming C3 plants, C3 fed terrestrial animals, and some freshwater resources. Current investigation demonstrated social differences between elites and country people and is promising in paleodietary and daily life reconstruction. Acknowledgement I thank prof. dr. G. Grupe, Director of the Anthropological and Palaeoanatomical State Collection in Munich for providing the opportunity to work in her laboratory. The part of this work was funded by DAAD. Antanaitis-Jacobs, Indre, et al. "Diet in early Lithuanian prehistory and the new stable isotope evidence." Archaeologia Baltica 12 (2009): 12-30. Le Huray, Jonathan D., and Holger Schutkowski. "Diet and social status during the La Tène period in Bohemia: carbon and nitrogen stable isotope analysis of bone collagen from Kutná Hora-Karlov and Radovesice." Journal of Anthropological Archaeology 24.2 (2005): 135-147. Schutkowski, Holger, et al. "Diet, status and decomposition at Weingarten: trace element and isotope analyses on early mediaeval skeletal material." Journal of Archaeological Science 26.6 (1999): 675-685. Zernitskaya, Valentina, et al. "Vegetation pattern and sedimentation changes in the context of the Lateglacial climatic events: Case study of Staroje Lake (Eastern Belarus)." Quaternary International (2014).

  8. Intestinal adenomas can develop with a stable karyotype and stable microsatellites

    E-print Network

    Dove, William

    of tumorigenesis in this organ. We find that tumors from C57BL 6 Min mice have a stable karyotype and stable metabolism and cellular homeostasis, the molecular bases of which are under intense scrutiny. Current models at least 11,000 genomic alterations (1). Given that the basal spontaneous mutation rate is unlikely

  9. Development of a Safety Management Web Tool for Horse Stables.

    PubMed

    Leppälä, Jarkko; Kolstrup, Christina Lunner; Pinzke, Stefan; Rautiainen, Risto; Saastamoinen, Markku; Särkijärvi, Susanna

    2015-01-01

    Managing a horse stable involves risks, which can have serious consequences for the stable, employees, clients, visitors and horses. Existing industrial or farm production risk management tools are not directly applicable to horse stables and they need to be adapted for use by managers of different types of stables. As a part of the InnoEquine project, an innovative web tool, InnoHorse, was developed to support horse stable managers in business, safety, pasture and manure management. A literature review, empirical horse stable case studies, expert panel workshops and stakeholder interviews were carried out to support the design. The InnoHorse web tool includes a safety section containing a horse stable safety map, stable safety checklists, and examples of good practices in stable safety, horse handling and rescue planning. This new horse stable safety management tool can also help in organizing work processes in horse stables in general. PMID:26569319

  10. Stable Phase Field Approximations of Anisotropic Solidification

    E-print Network

    Barrett, John W; Nürnberg, Robert

    2012-01-01

    We introduce unconditionally stable finite element approximations for a phase field model for solidification, which take highly anisotropic surface energy and kinetic effects into account. We hence approximate Stefan problems with anisotropic Gibbs--Thomson law with kinetic undercooling, and quasi-static variants thereof. The phase field model is given by {align*} \\vartheta\\,w_t + \\lambda\\,\\varrho(\\varphi)\\,\\varphi_t & = \

  11. Kinetic Stable Delaunay Graphs Pankaj K. Agarwal

    E-print Network

    Guibas, Leonidas J.

    Kinetic Stable Delaunay Graphs Pankaj K. Agarwal Duke University Jie Gao SUNY Stony Brook Leonidas are at least . We prove several interesting properties of SDG and describe two kinetic data structures Terms Algorithms, Theory Keywords Delaunay triangulation, Voronoi diagram, kinetic data structures 1

  12. MANIPULATION OF STABLE MATCHINGS USING MINIMAL BLACKLISTS

    E-print Network

    Hart, Sergiu

    -MAIL: ratio@math.huji.ac.il URL: http://www.ratio.huji.ac.il/ #12;Manipulation of Stable Matchings using Acceptance; Manipulation; Blacklist Einstein Institute of Mathematics and Center for the Study (Abdulkadiroglu et al., 2005a,b), to centralizing kidney donation assignments (Roth et al., 2005). In Gale

  13. Nuclear Structure: From Stable to Unstable Nuclei

    NASA Astrophysics Data System (ADS)

    Voronov, V. V.

    2015-11-01

    A finite rank separable approximation for Skyrme interactions is applied to study the collective nuclear modes in stable and unstable nuclei. The coupling between one- and two-phonon terms in the wave functions are taken into account. Some possibilities for experimental investigations of the manifestations of the pseudospin symmetry in the spectra of odd nuclei with Z ? 100 are indicated.

  14. UNCERTAINTY IN SOURCE PARTITIONING USING STABLE ISOTOPES

    EPA Science Inventory

    Stable isotope analyses are often used to quantify the contribution of multiple sources to a mixture, such as proportions of food sources in an animal's diet, C3 vs. C4 plant inputs to soil organic carbon, etc. Linear mixing models can be used to partition two sources with a sin...

  15. Substitution of stable isotopes in Chlorella

    NASA Technical Reports Server (NTRS)

    Flaumenhaft, E.; Katz, J. J.; Uphaus, R. A.

    1969-01-01

    Replacement of biologically important isotopes in the alga Chlorella by corresponding heavier stable isotopes produces increasingly greater deviations from the normal cell size and changes the quality and distribution of certain cellular components. The usefulness of isotopically altered organisms increases interest in the study of such permuted organisms.

  16. Ultra-stable superconducting cavity maser oscillator

    NASA Technical Reports Server (NTRS)

    Strayer, Donald M. (Inventor); Dick: G. John (Inventor)

    1989-01-01

    An ultra-stable superconducting triple cavity ruby maser oscillator (10) is obtained by providing the oscillator with a superconducting quantum interference device (SQUID) (50), which measures the magnetic field at the ruby (14) and compensates for changes by adjusting the RF pump signal amplitude (42), thereby attaining stabilities of about four orders of magnitude greater than presently attainable.

  17. Stable Fly Project in Campo Grande, Brazil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Andrew Li, Jerry Hogsette, and Beto Perez de Leon, all USDA, and Lane Foil, LSU, are collaborating as consultants on an Embrapa-funded research project for the control of large stable fly populations associated with sugar cane production in Brazil. Our Brazilian counterpart, Dr. Paulo Cançado, is t...

  18. Dynamically stable magnetic suspension/bearing system

    DOEpatents

    Post, R.F.

    1996-02-27

    A magnetic bearing system contains magnetic subsystems which act together to support a rotating element in a state of dynamic equilibrium. However, owing to the limitations imposed by Earnshaw`s Theorem, the magnetic bearing systems to be described do not possess a stable equilibrium at zero rotational speed. Therefore, mechanical stabilizers are provided, in each case, to hold the suspended system in equilibrium until its speed has exceeded a low critical speed where dynamic effects take over, permitting the achievement of a stable equilibrium for the rotating object. A state of stable equilibrium is achieved above a critical speed by use of a collection of passive elements using permanent magnets to provide their magnetomotive excitation. The magnetic forces exerted by these elements, when taken together, levitate the rotating object in equilibrium against external forces, such as the force of gravity or forces arising from accelerations. At the same time, this equilibrium is made stable against displacements of the rotating object from its equilibrium position by using combinations of elements that possess force derivatives of such magnitudes and signs that they can satisfy the conditions required for a rotating body to be stably supported by a magnetic bearing system over a finite range of those displacements. 32 figs.

  19. Dynamically stable magnetic suspension/bearing system

    DOEpatents

    Post, Richard F. (Walnut Creek, CA)

    1996-01-01

    A magnetic bearing system contains magnetic subsystems which act together to support a rotating element in a state of dynamic equilibrium. However, owing to the limitations imposed by Earnshaw's Theorem, the magnetic bearing systems to be described do not possess a stable equilibrium at zero rotational speed. Therefore, mechanical stabilizers are provided, in each case, to hold the suspended system in equilibrium until its speed has exceeded a low critical speed where dynamic effects take over, permitting the achievement of a stable equilibrium for the rotating object. A state of stable equilibrium is achieved above a critical speed by use of a collection of passive elements using permanent magnets to provide their magnetomotive excitation. The magnetic forces exerted by these elements, when taken together, levitate the rotating object in equilibrium against external forces, such as the force of gravity or forces arising from accelerations. At the same time, this equilibrium is made stable against displacements of the rotating object from its equilibrium position by using combinations of elements that possess force derivatives of such magnitudes and signs that they can satisfy the conditions required for a rotating body to be stably supported by a magnetic bearing system over a finite range of those displacements.

  20. Tracking animal movements using stable isotopes

    E-print Network

    Holberton, Rebecca L.

    Tracking animal movements using stable isotopes Keith A. Hobson #12;Isotopes as endogenous markers.00 4.00 5.00 6.00 Deltadiet-tissue(permil) King Penguin Rockhopper Penguin Ring-billed Gull Great Skua Peregrine Falcon Garden Warbler Humboldt's Penguin King Penguin Rockhopper Penguin Common Cormorant European

  1. The Nature of Stable Insomnia Phenotypes

    PubMed Central

    Pillai, Vivek; Roth, Thomas; Drake, Christopher L.

    2015-01-01

    Study Objectives: We examined the 1-y stability of four insomnia symptom profiles: sleep onset insomnia; sleep maintenance insomnia; combined onset and maintenance insomnia; and neither criterion (i.e., insomnia cases that do not meet quantitative thresholds for onset or maintenance problems). Insomnia cases that exhibited the same symptom profile over a 1-y period were considered to be phenotypes, and were compared in terms of clinical and demographic characteristics. Design: Longitudinal. Setting: Urban, community-based. Participants: Nine hundred fifty-four adults with Diagnostic and Statistical Manual of Mental Disorders, Fifth Edition based current insomnia (46.6 ± 12.6 y; 69.4% female). Interventions: None. Measurements and results: At baseline, participants were divided into four symptom profile groups based on quantitative criteria. Follow-up assessment 1 y later revealed that approximately 60% of participants retained the same symptom profile, and were hence judged to be phenotypes. Stability varied significantly by phenotype, such that sleep onset insomnia (SOI) was the least stable (42%), whereas combined insomnia (CI) was the most stable (69%). Baseline symptom groups (cross-sectionally defined) differed significantly across various clinical indices, including daytime impairment, depression, and anxiety. Importantly, however, a comparison of stable phenotypes (longitudinally defined) did not reveal any differences in impairment or comorbid psychopathology. Another interesting finding was that whereas all other insomnia phenotypes showed evidence of an elevated wake drive both at night and during the day, the “neither criterion” phenotype did not; this latter phenotype exhibited significantly higher daytime sleepiness despite subthreshold onset and maintenance difficulties. Conclusions: By adopting a stringent, stability-based definition, this study offers timely and important data on the longitudinal trajectory of specific insomnia phenotypes. With the exception of daytime sleepiness, few clinical differences are apparent across stable phenotypes. Citation: Pillai V, Roth T, Drake CL. The nature of stable insomnia phenotypes. SLEEP 2015;38(1):127–138. PMID:25325468

  2. Development of a Safety Management Web Tool for Horse Stables

    PubMed Central

    Leppälä, Jarkko; Kolstrup, Christina Lunner; Pinzke, Stefan; Rautiainen, Risto; Saastamoinen, Markku; Särkijärvi, Susanna

    2015-01-01

    Simple Summary A new web tool for equine activities, InnoHorse, was developed to support horse stable managers in business, safety, pasture and manure management. The aim of the safety section of the web tool was to raise awareness of safety issues in daily horse stable activities. This section contains a safety checklist, stable safety map and good practices to support human health and horse welfare and to prevent injuries in horse-related activities. Reviews of the literature and statistics, empirical horse stable case studies, expert panel workshops and stakeholder interviews were utilized in designing the web tool. Abstract Managing a horse stable involves risks, which can have serious consequences for the stable, employees, clients, visitors and horses. Existing industrial or farm production risk management tools are not directly applicable to horse stables and they need to be adapted for use by managers of different types of stables. As a part of the InnoEquine project, an innovative web tool, InnoHorse, was developed to support horse stable managers in business, safety, pasture and manure management. A literature review, empirical horse stable case studies, expert panel workshops and stakeholder interviews were carried out to support the design. The InnoHorse web tool includes a safety section containing a horse stable safety map, stable safety checklists, and examples of good practices in stable safety, horse handling and rescue planning. This new horse stable safety management tool can also help in organizing work processes in horse stables in general. PMID:26569319

  3. Overview and first results from project STABLE (STAble Boundary Layer Experiment)

    SciTech Connect

    Weber, A.H.; Kurzeja, R.J.

    1988-01-01

    The STABLE project (STAble Boundary Layer Experiment) is a multiyear research effort conceived in 1984 by the Savannah River Laboratory (SRL) and planned by several research groups to study turbulence and diffusion in the stable boundary layer (SBL). The program was jointly planned by Department of Energy (DOE) affiliated laboratories and universities including SRL, Atmospheric Turbulence and Diffusion Division (ATDD) of the National Oceanic and Atmospheric Administration (NOAA), Argonne National Laboratory (ANL), North Carolina State University (NCSU), and The Pennsylvania State University. STABLE's goals are to determine the spatial and temporal distribution of turbulent events during the nighttime, to determine the validity of present models and theories in describing the structure and evolution of the SBL, to determine the role of waves and intermittent turbulence in dispersing chemicals, and to determine better parameterization for describing the mean state and intermittent events in the SBL. By taking advantage of special facility, the program seeks to economize effort and cost. 1 ref., 7 figs.

  4. Air-stable droplet interface bilayers

    NASA Astrophysics Data System (ADS)

    Collier, Charles; ORNL Team

    2015-03-01

    Droplet interface bilayers are versatile model membranes useful for synthetic biology and biosensing; however, to date they have been for the most part confined to fluid reservoirs. Here, we demonstrate that when two or more water droplets meet on an oil-infused substrate, they exhibit noncoalescence due to the formation of a thin oil film that gets squeezed between the droplets from the bottom up. We show that when phospholipids are included in the water droplets, a stable droplet interface bilayer forms between the noncoalescing water droplets. As with traditional oil-submerged droplet interface bilayers, we were able to characterize ion channel transport by incorporating peptides into each droplet. We demonstrate the ability of these air-stable droplet interface bilayers (airDIBs) to incorporate ligand-gated ion channels via fusion of microsomes, which enables the biosensing of airborne matter.

  5. Stable Lithium Argon compounds under high pressure

    NASA Astrophysics Data System (ADS)

    Li, Xiaofeng; Hermann, Andreas; Peng, Feng; Lv, Jian; Wang, Yanchao; Wang, Hui; Ma, Yanming

    2015-11-01

    High pressure can fundamentally alter the bonding patterns of chemical elements. Its effects include stimulating elements thought to be “inactive” to form unexpectedly stable compounds with unusual chemical and physical properties. Here, using an unbiased structure search method based on CALYPSO methodology and density functional total energy calculations, the phase stabilities and crystal structures of Li?Ar compounds are systematically investigated at high pressure up to 300?GPa. Two unexpected LimArn compounds (LiAr and Li3Ar) are predicted to be stable above 112?GPa and 119?GPa, respectively. A detailed analysis of the electronic structure of LiAr and Li3Ar shows that Ar in these compounds attracts electrons and thus behaves as an oxidizing agent. This is markedly different from the hitherto established chemical reactivity of Ar. Moreover, we predict that the P4/mmm phase of Li3Ar has a superconducting transition temperature of 17.6?K at 120?GPa.

  6. A stable Ti-based quasicrystal

    SciTech Connect

    Kelton, K.F.; Kim, W.J.; Stroud, R.M.

    1997-06-01

    The thermal stability of the icosahedral phase (i phase) in Ti{sub 45}Zr{sub 38}Ni{sub 17} alloys is demonstrated. As-cast alloys containing initially only the C14 hexagonal Laves and {alpha}-solid-solution phases transformed primarily to the icosahedral phase upon annealing in vacuum for 64 h at 570{degree}C. This confirms previous evidence for i-phase stability and firmly establishes this quasicrystal as the first nonaluminum stable icosahedral phase. Diffraction data show that this stable i phase is primitive; energy dispersive x-ray spectroscopy measurements place its composition near Ti{sub 41.5}Zr{sub 41.5}Ni{sub 17}. These and other results suggest that the structure of this i phase is similar to that of i(AlLiCu). {copyright} {ital 1997 American Institute of Physics.}

  7. Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates

    NASA Technical Reports Server (NTRS)

    Simpson, Joycely O. (Inventor); St.Clair, Terry L. (Inventor)

    1999-01-01

    A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

  8. Observation of stable-vector vortex solitons.

    PubMed

    Izdebskaya, Yana; Assanto, Gaetano; Krolikowski, Wieslaw

    2015-09-01

    We report on the first experimental observation of stable-vector vortex solitons in nonlocal nonlinear media with a reorientational response, such as nematic liquid crystals. These solitons consist of two co-polarized, mutually trapped beams of different colors, a bright fundamental spatial soliton, and a nonlinear optical vortex. The nonlinear vortex component, which is normally unstable in nonlinear media, is stabilized and confined here by the highly nonlocal refractive potential induced by the soliton. PMID:26368742

  9. Stable numerical boundary conditions for Stokes equations

    SciTech Connect

    Meth, K.Z. . Matam-Advanced Technology Center)

    1994-10-01

    The author works with the vorticity-stream function formulation of the Stokes equations. Two boundary conditions are given for the stream function while no boundary conditions are given for the vorticity. A derived boundary condition for the vorticity is considered and it is proven that the resulting fully discrete numerical method is stable. The results are then extended to the three-dimensional Stokes equations using a staggered grid.

  10. Stable Spheromaks Sustained by Neutral Beam Injection

    SciTech Connect

    Fowler, T K; Jayakumar, R; McLean, H S

    2008-05-14

    It is shown that spheromak equilibria, stable at zero-beta but departing from the Taylor state, could be sustained by non-inductive current drive at acceptable power levels. Stability to both ideal MHD and tearing modes is verified using the NIMROD code for linear stability analysis. Non-linear NIMROD calculations with non-inductive current drive and pressure effects could point the way to improved fusion reactors.

  11. Quantifying uncertainty in stable isotope mixing models

    NASA Astrophysics Data System (ADS)

    Davis, Paul; Syme, James; Heikoop, Jeffrey; Fessenden-Rahn, Julianna; Perkins, George; Newman, Brent; Chrystal, Abbey E.; Hagerty, Shannon B.

    2015-05-01

    Mixing models are powerful tools for identifying biogeochemical sources and determining mixing fractions in a sample. However, identification of actual source contributors is often not simple, and source compositions typically vary or even overlap, significantly increasing model uncertainty in calculated mixing fractions. This study compares three probabilistic methods, Stable Isotope Analysis in R (SIAR), a pure Monte Carlo technique (PMC), and Stable Isotope Reference Source (SIRS) mixing model, a new technique that estimates mixing in systems with more than three sources and/or uncertain source compositions. In this paper, we use nitrate stable isotope examples (?15N and ?18O) but all methods tested are applicable to other tracers. In Phase I of a three-phase blind test, we compared methods for a set of six-source nitrate problems. PMC was unable to find solutions for two of the target water samples. The Bayesian method, SIAR, experienced anchoring problems, and SIRS calculated mixing fractions that most closely approximated the known mixing fractions. For that reason, SIRS was the only approach used in the next phase of testing. In Phase II, the problem was broadened where any subset of the six sources could be a possible solution to the mixing problem. Results showed a high rate of Type I errors where solutions included sources that were not contributing to the sample. In Phase III some sources were eliminated based on assumed site knowledge and assumed nitrate concentrations, substantially reduced mixing fraction uncertainties and lowered the Type I error rate. These results demonstrate that valuable insights into stable isotope mixing problems result from probabilistic mixing model approaches like SIRS. The results also emphasize the importance of identifying a minimal set of potential sources and quantifying uncertainties in source isotopic composition as well as demonstrating the value of additional information in reducing the uncertainty in calculated mixing fractions.

  12. Stable freestanding thin films of pure water

    SciTech Connect

    Weon, B. M.; Je, J. H.; Hwu, Y.; Margaritondo, G.

    2008-03-10

    Obtaining water microstructures is very difficult because of low viscosity and high surface tension. We produced stable freestanding thin films of pure water by x-ray bombardment of small liquid volumes in capillary tubes. A detailed characterization with phase-contrast radiology demonstrated a lifetime beyond 1 h with no chemical stabilizer for micron-thickness films with half-millimeter-level diameter. This can be attributed to the interplay of two x-ray effects: water evaporation and surface charging.

  13. Is Bitcoin Stable, Secure and Scalable?

    E-print Network

    ;The Blockchain Time #12;The Blockchain Time #12;Is Bitcoin stable? #12;The Blockchain Time #12;The Blockchain Time #12;Propagation Speed 0 10 20 30 40 50 60 Time since first observation [s] 0.00 0.02 0.04 0://bitcoinstats.com #12;Blockchain Forks 180000 182000 184000 186000 188000 190000 Blockchain Height 0 2 4 6 8 10 12 Forks

  14. Deformed Palmprint Matching Based on Stable Regions.

    PubMed

    Wu, Xiangqian; Zhao, Qiushi

    2015-12-01

    Palmprint recognition (PR) is an effective technology for personal recognition. A main problem, which deteriorates the performance of PR, is the deformations of palmprint images. This problem becomes more severe on contactless occasions, in which images are acquired without any guiding mechanisms, and hence critically limits the applications of PR. To solve the deformation problems, in this paper, a model for non-linearly deformed palmprint matching is derived by approximating non-linear deformed palmprint images with piecewise-linear deformed stable regions. Based on this model, a novel approach for deformed palmprint matching, named key point-based block growing (KPBG), is proposed. In KPBG, an iterative M-estimator sample consensus algorithm based on scale invariant feature transform features is devised to compute piecewise-linear transformations to approximate the non-linear deformations of palmprints, and then, the stable regions complying with the linear transformations are decided using a block growing algorithm. Palmprint feature extraction and matching are performed over these stable regions to compute matching scores for decision. Experiments on several public palmprint databases show that the proposed models and the KPBG approach can effectively solve the deformation problem in palmprint verification and outperform the state-of-the-art methods. PMID:26390453

  15. Charge Radii of beta-Stable Nuclei

    E-print Network

    G. K. Nie

    2005-12-07

    In previous work it was shown that the radius of nucleus R is determined by the alpha-cluster structure and can be estimated on the number of alpha-clusters disregarding to the number of excess neutrons. A hypothesis also was made that the radius R_m of a beta-stable isotope, which is actually measured at electron scattering experiments, is determined by the volume occupied by the matter of the core plus the volume occupied by the peripheral alpha-clusters. In this paper it is shown that the condition R_m = R restricts the number of excess neutrons filling the core to provide the beta-stability. The number of peripheral clusters can vary from 1 to 5 and the value of R for heavy nuclei almost do not change, whereas the number of excess neutrons should change with the number of peripheral clusters to get the value of R_m close to R. It can explain the path of the beta-stability and its width. The radii R_m of the stable isotopes with 12 =< Z =< 83 and the alpha-decay isotopes with 84 =< Z =< 116 that are stable to beta-decay have been calculated.

  16. Detonation of Meta-stable Clusters

    SciTech Connect

    Kuhl, Allen; Kuhl, Allen L.; Fried, Laurence E.; Howard, W. Michael; Seizew, Michael R.; Bell, John B.; Beckner, Vincent; Grcar, Joseph F.

    2008-05-31

    We consider the energy accumulation in meta-stable clusters. This energy can be much larger than the typical chemical bond energy (~;;1 ev/atom). For example, polymeric nitrogen can accumulate 4 ev/atom in the N8 (fcc) structure, while helium can accumulate 9 ev/atom in the excited triplet state He2* . They release their energy by cluster fission: N8 -> 4N2 and He2* -> 2He. We study the locus of states in thermodynamic state space for the detonation of such meta-stable clusters. In particular, the equilibrium isentrope, starting at the Chapman-Jouguet state, and expanding down to 1 atmosphere was calculated with the Cheetah code. Large detonation pressures (3 and 16 Mbar), temperatures (12 and 34 kilo-K) and velocities (20 and 43 km/s) are a consequence of the large heats of detonation (6.6 and 50 kilo-cal/g) for nitrogen and helium clusters respectively. If such meta-stable clusters could be synthesized, they offer the potential for large increases in the energy density of materials.

  17. Coinage metals binding as main group elements: structure and bonding of the carbene complexes [TM(cAAC)2] and [TM(cAAC)2](+) (TM = Cu, Ag, Au).

    PubMed

    Jerabek, Paul; Roesky, Herbert W; Bertrand, Guy; Frenking, Gernot

    2014-12-10

    Quantum chemical calculations using density functional theory have been carried out for the cyclic (alkyl)(amino)carbene (cAAC) complexes of the group 11 atoms [TM(cAAC)2] (TM = Cu, Ag, Au) and their cations [TM(cAAC)2](+). The nature of the metal-ligand bonding was investigated with the charge and energy decomposition analysis EDA-NOCV. The calculations show that the TM-C bonds in the charged adducts [TM(cAAC)2](+) are significantly longer than in the neutral complexes [TM(cAAC)2], but the cations have much higher bond dissociation energies than the neutral molecules. The intrinsic interaction energies ?Eint in [TM(cAAC)2](+) take place between TM(+) in the (1)S electronic ground state and (cAAC)2. In contrast, the metal-ligand interactions in [TM(cAAC)2] involve the TM atoms in the excited (1)P state yielding strong TM p(?) ? (cAAC)2 ? backdonation, which is absent in the cations. The calculations suggest that the cAAC ligands in [TM(cAAC)2] are stronger ? acceptors than ? donors. The trends of the intrinsic interaction energies and the bond dissociation energies of the metal-ligand bonds in [TM(cAAC)2] and [TM(cAAC)2](+) give the order Au > Cu > Ag. Calculations at the nonrelativistic level give weaker TM-C bonds, particularly for the gold complexes. The trend for the bond strength in the neutral and charged adducts without relativistic effects becomes Cu > Ag > Au. The EDA-NOCV calculations suggest that the weaker bonds at the nonrelativistic level are mainly due to stronger Pauli repulsion and weaker orbital interactions. The NBO picture of the C-TM-C bonding situation does not correctly represent the nature of the metal-ligand interactions in [TM(cAAC)2]. PMID:25394669

  18. Ruthenium(II) and osmium(II) complexes bearing bipyridine and the N-heterocyclic carbene-based C^N^C pincer ligand: an experimental and density functional theory study.

    PubMed

    Chung, Lai-Hon; Cho, Ka-Sin; England, Jason; Chan, Siu-Chung; Wieghardt, Karl; Wong, Chun-Yuen

    2013-09-01

    Ruthenium(II) and osmium(II) complexes [M(C^N^C)(N^N)L](n+) (L = Cl(-), n = 1; L = CH3CN, t-BuNC, n = 2) containing a neutral tridentate N-heterocyclic carbene (NHC)-based pincer ligand, either 2,6-bis(1-butylimidazol-2-ylidene)pyridine (C(1)^N^C(1)) or 2,6-bis(3-butylbenzimidazol-2-ylidene)pyridine (C(2)^N^C(2)), and a neutral 2,2'-bipyridine-type aromatic diimine have been prepared. Investigations into the effects of varying M (Ru and Os), C^N^C, N^N, and L on the structural, electrochemical, absorption, and emission characteristics associated with [M(C^N^C)(N^N)L](n+) are presented. Interestingly, spectroscopic findings and time-dependent density functional theory (TD-DFT) calculations in this work support a d?(Ru(II)/Os(II)) ? ?*(N^N) metal-to-ligand charge transfer (MLCT) assignment for the lowest-energy transition in [M(C^N^C)(N^N)L](n+) and not a d?(Ru(II)/Os(II)) ? ?*(C^N^C) MLCT assignment. This is in stark contrast to [Ru(tpy)(bpy)Cl](+) and [Os(tpy)(bpy)Cl](+) (tpy = 2,2':6',2?-terpyridine, bpy = 2,2'-bipyridine) for which the lowest-energy transitions are assigned as d?(Ru/Os) ? ?*(tpy) MLCT transitions. [Ru(II)(C^N^C)(N^N)L](n+) is emissive with emission maxima of around 600-700 nm observed upon photoexcitation of their d?(Ru(II)) ? ?*(N^N) MLCT bands. The electronic structures for [Ru(C^N^C)(N^N)Cl](0) have also been probed by spectroelectrochemistry, electron paramagnetic resonance (EPR) spectroscopy, and DFT calculations, which reveal that the lowest unoccupied molecular orbitals (LUMOs) for [Ru(C^N^C)(N^N)Cl](+) are N^N-based. PMID:23952294

  19. N-Heterocyclic Carbene-Copper-Catalyzed Group-, Site-, and Enantioselective Allylic Substitution with a Readily Accessible Propargyl(pinacolato)boron Reagent: Utility in Stereoselective Synthesis and Mechanistic Attributes.

    PubMed

    Shi, Ying; Jung, Byunghyuck; Torker, Sebastian; Hoveyda, Amir H

    2015-07-22

    The first instances of catalytic allylic substitution reactions involving a propargylic nucleophilic component are presented; reactions are facilitated by 5.0 mol % of a catalyst derived from a chiral N-heterocyclic carbene (NHC) and a copper chloride salt. A silyl-containing propargylic organoboron compound, easily prepared in multigram quantities, serves as the reagent. Aryl- and heteroaryl-substituted disubstituted alkenes within allylic phosphates and those with an alkyl or a silyl group can be used. Functional groups typically sensitive to hard nucleophilic reagents are tolerated, particularly in the additions to disubstituted alkenes. Reactions may be performed on the corresponding trisubstituted alkenes, affording quaternary carbon stereogenic centers. Incorporation of the propargylic group is generally favored (vs allenyl addition; 89:11 to >98:2 selectivity); 1,5-enynes can be isolated in 75-90% yield, 87:13 to >98:2 SN2'/SN2 (branched/linear) selectivity and 83:17-99:1 enantiomeric ratio. Utility is showcased by conversion of the alkynyl group to other useful functional units (e.g., homoallenyl and Z-homoalkenyl iodide), direct access to which by other enantioselective protocols would otherwise entail longer routes. Application to stereoselective synthesis of the acyclic portion of antifungal agent plakinic acid A, containing two remotely positioned stereogenic centers, by sequential use of two different NHC-Cu-catalyzed enantioselective allylic substitution (EAS) reactions further highlights utility. Mechanistic investigations (density functional theory calculations and deuterium labeling) point to a bridging function for an alkali metal cation connecting the sulfonate anion and a substrate's phosphate group to form the branched propargyl addition products as the dominant isomers via Cu(III) ?-allyl intermediate complexes. PMID:26172476

  20. Mössbauer, electron paramagnetic resonance, and theoretical studies of a carbene-based all-ferrous Fe4S4 cluster: electronic origin and structural identification of the unique spectroscopic site.

    PubMed

    Chakrabarti, Mrinmoy; Deng, Liang; Holm, R H; Münck, Eckard; Bominaar, Emile L

    2009-04-01

    It is well established that the cysteinate-coordinated [Fe(4)S(4)] cluster of the iron protein of nitrogenase from Azotobacter vinelandii (Av2) can attain the all-ferrous core oxidation state. Mössbauer and electron paramagnetic resonance (EPR) studies have shown that the all-ferrous cluster has a ground-state spin S = 4 and an effective 3:1 site symmetry in the spin structure and (57)Fe quadrupole interactions. Recently, Deng and Holm reported the synthesis of [Fe(4)S(4)(Pr(i)(2)NHCMe(2))(4)],(2) (1; Pr(i)(2)NHCMe(2) = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) and showed that the all-ferrous carbene-coordinated cluster is amenable to physicochemical studies. Mössbauer and EPR studies of 1, reported here, reveal that the electronic structure of this complex is strikingly similar to that of the protein-bound cluster, suggesting that the ground-state spin and the 3:1 site ratio are consequences of spontaneous distortions of the cluster core. To gain insight into the origin of the peculiar ground state of the all-ferrous clusters in 1 and Av2, we have studied a theoretical model that is based on a Heisenberg-Dirac-van Vleck Hamiltonian whose exchange-coupling constants are a function of the Fe-Fe distances. By combining the exchange energies with the elastic deformation energies in the harmonic approximation, we obtain for a T(2) distortion a minimum with spin S = 4 and a C(3v) core structure in which one iron is unique and three irons are equivalent. This minimum has all of the spectroscopic and structural characteristics of the all-ferrous clusters of 1 and Av2. Our analysis maps the unique spectroscopic iron site to a specific site in the X-ray structure of the [Fe(4)S(4)](0) core both in complex 1 and in Av2. PMID:19326927

  1. Isotropic turbulence, stable layers: facts or fictions?

    NASA Astrophysics Data System (ADS)

    Lovejoy, S.; Tuck, A.; Hovde, S.; Schertzer, D.

    2007-05-01

    Using state of the art drop sonde data (from 237 sondes over the Pacific) we examine two classical and fundamental idealizations of atmospheric science showing that they are untenable in the light of the vertical structure. The first is the notion of stable atmospheric layers. This is used for understanding atmospheric dynamics and thermodynamics, including the most advanced dynamical meteorological notions such as potential vorticity. Using the drop sonde data, we show that each apparently stable layer is actually composed of a hierarchy of unstable layers themselves with embedded stable sublayers, each with unstable sub-sub layers etc. i.e. in a Russian doll-like fractal hierarchy whose dimension we estimate. We therefore argue that the notion is untenable and must be replaced by modern scaling notions. The second idealization we examine is the turbulence assumption of isotropy. If we include intermittency, Kolmorogov's landmark proposal that fully developed turbulence has an "inertial subrange" with isotropic energy spectrum E(k)=k**-beta with beta=5/3 has apparently been spectacularly confirmed in both the horizontal direction and in the time domain (k is a wavenumber). For gradients over a horizontal distance deltax this implies deltav=deltaz**Hh (Hh=1/3 corresponds to beta=5/3). Remarkably, Hv for gradients over vertical distances deltaz (deltav=deltaz**Hv) has not been seriously investigated. Using drop sonde data of horizontal wind, we find that from scales of 5 m to 10 km from the surface layer through to the top of the troposphere, Hv is close to (or larger) than the Bolgiano-Obukhov value 3/5. Hv greater than Hh implies that a) the atmosphere becomes progressively less stratified at smaller scales although in a scaling way; b) that at most a single (roughly) isotropic "sphero- scale" exists (often in the range 1-100 cm).

  2. Quantifying uncertainty in stable isotope mixing models

    DOE PAGESBeta

    Davis, Paul; Syme, James; Heikoop, Jeffrey; Fessenden-Rahn, Julianna; Perkins, George; Newman, Brent; Chrystal, Abbey E.; Hagerty, Shannon B.

    2015-05-19

    Mixing models are powerful tools for identifying biogeochemical sources and determining mixing fractions in a sample. However, identification of actual source contributors is often not simple, and source compositions typically vary or even overlap, significantly increasing model uncertainty in calculated mixing fractions. This study compares three probabilistic methods, SIAR [Parnell et al., 2010] a pure Monte Carlo technique (PMC), and Stable Isotope Reference Source (SIRS) mixing model, a new technique that estimates mixing in systems with more than three sources and/or uncertain source compositions. In this paper, we use nitrate stable isotope examples (?15N and ?18O) but all methods testedmore »are applicable to other tracers. In Phase I of a three-phase blind test, we compared methods for a set of six-source nitrate problems. PMC was unable to find solutions for two of the target water samples. The Bayesian method, SIAR, experienced anchoring problems, and SIRS calculated mixing fractions that most closely approximated the known mixing fractions. For that reason, SIRS was the only approach used in the next phase of testing. In Phase II, the problem was broadened where any subset of the six sources could be a possible solution to the mixing problem. Results showed a high rate of Type I errors where solutions included sources that were not contributing to the sample. In Phase III some sources were eliminated based on assumed site knowledge and assumed nitrate concentrations, substantially reduced mixing fraction uncertainties and lowered the Type I error rate. These results demonstrate that valuable insights into stable isotope mixing problems result from probabilistic mixing model approaches like SIRS. The results also emphasize the importance of identifying a minimal set of potential sources and quantifying uncertainties in source isotopic composition as well as demonstrating the value of additional information in reducing the uncertainty in calculated mixing fractions.« less

  3. Quantitative Microbial Ecology through Stable Isotope Probing.

    PubMed

    Hungate, Bruce A; Mau, Rebecca L; Schwartz, Egbert; Caporaso, J Gregory; Dijkstra, Paul; van Gestel, Natasja; Koch, Benjamin J; Liu, Cindy M; McHugh, Theresa A; Marks, Jane C; Morrissey, Ember M; Price, Lance B

    2015-11-01

    Bacteria grow and transform elements at different rates, and as yet, quantifying this variation in the environment is difficult. Determining isotope enrichment with fine taxonomic resolution after exposure to isotope tracers could help, but there are few suitable techniques. We propose a modification to stable isotope probing (SIP) that enables the isotopic composition of DNA from individual bacterial taxa after exposure to isotope tracers to be determined. In our modification, after isopycnic centrifugation, DNA is collected in multiple density fractions, and each fraction is sequenced separately. Taxon-specific density curves are produced for labeled and nonlabeled treatments, from which the shift in density for each individual taxon in response to isotope labeling is calculated. Expressing each taxon's density shift relative to that taxon's density measured without isotope enrichment accounts for the influence of nucleic acid composition on density and isolates the influence of isotope tracer assimilation. The shift in density translates quantitatively to isotopic enrichment. Because this revision to SIP allows quantitative measurements of isotope enrichment, we propose to call it quantitative stable isotope probing (qSIP). We demonstrated qSIP using soil incubations, in which soil bacteria exhibited strong taxonomic variations in (18)O and (13)C composition after exposure to [(18)O]water or [(13)C]glucose. The addition of glucose increased the assimilation of (18)O into DNA from [(18)O]water. However, the increase in (18)O assimilation was greater than expected based on utilization of glucose-derived carbon alone, because the addition of glucose indirectly stimulated bacteria to utilize other substrates for growth. This example illustrates the benefit of a quantitative approach to stable isotope probing. PMID:26296731

  4. Quantifying uncertainty in stable isotope mixing models

    SciTech Connect

    Davis, Paul; Syme, James; Heikoop, Jeffrey; Fessenden-Rahn, Julianna; Perkins, George; Newman, Brent; Chrystal, Abbey E.; Hagerty, Shannon B.

    2015-05-19

    Mixing models are powerful tools for identifying biogeochemical sources and determining mixing fractions in a sample. However, identification of actual source contributors is often not simple, and source compositions typically vary or even overlap, significantly increasing model uncertainty in calculated mixing fractions. This study compares three probabilistic methods, SIAR [Parnell et al., 2010] a pure Monte Carlo technique (PMC), and Stable Isotope Reference Source (SIRS) mixing model, a new technique that estimates mixing in systems with more than three sources and/or uncertain source compositions. In this paper, we use nitrate stable isotope examples (?15N and ?18O) but all methods tested are applicable to other tracers. In Phase I of a three-phase blind test, we compared methods for a set of six-source nitrate problems. PMC was unable to find solutions for two of the target water samples. The Bayesian method, SIAR, experienced anchoring problems, and SIRS calculated mixing fractions that most closely approximated the known mixing fractions. For that reason, SIRS was the only approach used in the next phase of testing. In Phase II, the problem was broadened where any subset of the six sources could be a possible solution to the mixing problem. Results showed a high rate of Type I errors where solutions included sources that were not contributing to the sample. In Phase III some sources were eliminated based on assumed site knowledge and assumed nitrate concentrations, substantially reduced mixing fraction uncertainties and lowered the Type I error rate. These results demonstrate that valuable insights into stable isotope mixing problems result from probabilistic mixing model approaches like SIRS. The results also emphasize the importance of identifying a minimal set of potential sources and quantifying uncertainties in source isotopic composition as well as demonstrating the value of additional information in reducing the uncertainty in calculated mixing fractions.

  5. Shear viscosity of $?$-stable nuclear matter

    E-print Network

    Omar Benhar; Arianna Carbone

    2009-12-01

    Viscosity plays a critical role in determining the stability of rotating neutron stars. We report the results of a calculation of the shear viscosity of $\\beta$~-~stable matter, carried out using an effective interaction based on a state-of-the-art nucleon-nucleon potential and the formalism of correlated basis functions. Within our approach the equation of state, determining the proton fraction, and the nucleon-nucleon scattering probability are consistently obtained from the same dynamical model. The results show that, while the neutron contribution to the viscosity is always dominant, above nuclear saturation density the electron contribution becomes appreciable.

  6. Generation of stable overlaps between antiparallel filaments

    E-print Network

    Johann, D; Kruse, K

    2015-01-01

    During cell division, sister chromatids are segregated by the mitotic spindle, a bipolar assembly of interdigitating antiparallel polar filaments called microtubules. Establishing a stable overlap region is essential for maintenance of bipolarity, but the underlying mechanisms are poorly understood. Using a particle-based stochastic model, we find that the interplay of motors and passive cross linkers can robustly generate partial overlaps between antiparallel filaments. Our analysis shows that motors reduce the overlap in a length-dependent manner, whereas passive cross linkers increase it independently of the length. In addition to maintaining structural integrity, passive cross linkers can thus also have a dynamic role for size regulation.

  7. Generation of Stable Overlaps between Antiparallel Filaments

    NASA Astrophysics Data System (ADS)

    Johann, D.; Goswami, D.; Kruse, K.

    2015-09-01

    During cell division, sister chromatids are segregated by the mitotic spindle, a bipolar assembly of interdigitating antiparallel polar filaments called microtubules. Establishing a stable overlap region is essential for maintenance of bipolarity, but the underlying mechanisms are poorly understood. Using a particle-based stochastic model, we find that the interplay of motors and passive cross-linkers can robustly generate partial overlaps between antiparallel filaments. In this situation, motors reduce the overlap in a length-dependent manner, whereas passive cross-linkers increase it independently of the length. In addition to maintaining structural integrity, passive cross-linkers can thus also have a dynamic role for overlap size regulation.

  8. Stable metallization for diamond and other materials

    NASA Technical Reports Server (NTRS)

    Bachli, Andreas (Inventor); Kolawa, Elzbieta (Inventor); Nicolet, Marc-Aurele (Inventor); Vandersande, Jan W. (Inventor)

    2000-01-01

    An adherent and metallurgically stable metallization system for diamond is presented. The big improvement in metallurgical stability is attributed to the use of a ternary, amorphous Ti--Si--N diffusion barrier. No diffusion between the layers and no delamination of the metallization was observed after annealing the schemes at 400.degree. C. for 100 hours and at 900.degree. C. for 30 minutes. Thermal cycling experiments in air from -65 to 155.degree. C. and adhesion tests were performed. Various embodiments are disclosed.

  9. Generation of stable overlaps between antiparallel filaments

    E-print Network

    D. Johann; D. Goswami; K. Kruse

    2015-03-26

    During cell division, sister chromatids are segregated by the mitotic spindle, a bipolar assembly of interdigitating antiparallel polar filaments called microtubules. Establishing a stable overlap region is essential for maintenance of bipolarity, but the underlying mechanisms are poorly understood. Using a particle-based stochastic model, we find that the interplay of motors and passive cross linkers can robustly generate partial overlaps between antiparallel filaments. Our analysis shows that motors reduce the overlap in a length-dependent manner, whereas passive cross linkers increase it independently of the length. In addition to maintaining structural integrity, passive cross linkers can thus also have a dynamic role for size regulation.

  10. Stable quark matter in cosmic rays?

    E-print Network

    Jes Madsen

    2005-12-20

    Stable lumps of quark matter may be present in cosmic rays at a flux level, which can be detected by high precision cosmic ray experiments sensitive to anomalous "nuclei" with high mass-to-charge ratio. The properties of these lumps, called strangelets, are described, and so is the production and propagation of strangelets in cosmic rays. Two experiments underway which are sensitive to a strangelet flux in the predicted range are briefly described. Finally it is summarized how strangelets circumvent the acceleration problem encountered by conventional candidates for ultra-high energy cosmic rays and move the Greisen-Zatsepin-Kuzmin cutoff to energies well above the observed maximum energies.

  11. Stable parallel elimination for boundary valve ODEs

    SciTech Connect

    Wright, S.J.

    1991-04-01

    A parallelizable and vectorizable algorithm for solving linear algebraic systems arising from two-point boundary value ODEs is described. The method is equivalent to Gaussian elimination, with row partial pivoting, applied to a certain row- and column-reordered version of the usual almost block-diagonal coefficient matrix. Analytical and numerical evidence is presented to show that the algorithm is stable. Results from implementation on a shared-memory multiprocessor and a vector processor are given. The approach can be extended to handle problems with multipoint and integral conditions or algebraic parameters.

  12. Medical management of chronic stable angina

    PubMed Central

    Wee, Yong; Burns, Kylie; Bett, Nicholas

    2015-01-01

    Summary Stable angina pectoris is characterised by typical exertional chest pain that is relieved by rest or nitrates. Risk stratification of patients is important to define prognosis, to guide medical management and to select patients suitable for revascularisation. Medical treatment aims to relieve angina and prevent cardiovascular events. Beta blockers and calcium channel antagonists are first-line options for treatment. Short-acting nitrates can be used for symptom relief. Low-dose aspirin and statins are prescribed to prevent cardiovascular events. PMID:26648642

  13. Stable isotope (18 C) sclerochronology of Callovian (Middle

    E-print Network

    Schöne, Bernd R.

    Stable isotope (18 O and 13 C) sclerochronology of Callovian (Middle Jurassic) bivalves (Gryphaea January 2014 Keywords: Jurassic Paleoseasonality Gryphaea Belemnite Oxygen and carbon stable isotopes from G. (B.) dilobotes, with 13 C depletion occurring during warmer periods, possibly related

  14. 2. Historic American Buildings Survey 'Stable and Smoke House' Photocopy ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    2. Historic American Buildings Survey 'Stable and Smoke House' Photocopy of Plate XXX From: Brown, Glenn, The Octagon, Washington, N.D. - Octagon House, Stable, 1799 New York Avenue Northwest, Washington, District of Columbia, DC

  15. Stable interior, showing center aisle, stalls, and feed troughs. View ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Stable interior, showing center aisle, stalls, and feed troughs. View looking southwest - Fort Hill Farm, Stable, West of Staunton (Roanoke) River between Turkey & Caesar's Runs, Clover, Halifax County, VA

  16. Stable magnesium peroxide at high pressure

    NASA Astrophysics Data System (ADS)

    Lobanov, Sergey S.; Zhu, Qiang; Holtgrewe, Nicholas; Prescher, Clemens; Prakapenka, Vitali B.; Oganov, Artem R.; Goncharov, Alexander F.

    2015-09-01

    Rocky planets are thought to comprise compounds of Mg and O as these are among the most abundant elements, but knowledge of their stable phases may be incomplete. MgO is known to be remarkably stable to very high pressure and chemically inert under reduced condition of the Earth’s lower mantle. However, in exoplanets oxygen may be a more abundant constituent. Here, using synchrotron x-ray diffraction in laser-heated diamond anvil cells, we show that MgO and oxygen react at pressures above 96?GPa and T?=?2150?K with the formation of I4/mcm MgO2. Raman spectroscopy detects the presence of a peroxide ion (O22-) in the synthesized material as well as in the recovered specimen. Likewise, energy-dispersive x-ray spectroscopy confirms that the recovered sample has higher oxygen content than pure MgO. Our finding suggests that MgO2 may be present together or instead of MgO in rocky mantles and rocky planetary cores under highly oxidized conditions.

  17. Electrochemical Fractionation of Molybdenum Stable Isotopes

    NASA Astrophysics Data System (ADS)

    Crawford, J.; Black, J.; Wasylenki, L.; Gordon, G.; Anbar, A.; Kavner, A.

    2008-12-01

    Stable isotope signatures were measured from Molybdenum (Mo) electrodeposited from aqueous solution. As potential varied from -1.35 V to -2.00 V (relative to Ag/AgCl), fractionation decreases from ?97/95Mo = -1.3 ‰ to -0.9 ‰ (?97/95Mo defined as the difference in the 97Mo/95Mo ratio of deposited Mo relative to aqueous Mo). Natural variations of ?97/95Mo span a range of ~ 3 ‰ [Barling, J. and Anbar, A. D., EPSL. 2004, 217: 315], therefore, charge transfer driven fractionation may be responsible for some of the observed variation in Mo stable isotope geochemistry. Following previous approaches with Fe and Zn [Kavner, A. et al. Geochim. Cosmochim. Acta. 2005, 69: 2971; 2008, 72: 1731], Mo was plated in a three-electrode cell from a neutral to slightly alkaline solution (pH ~ 8.7). Voltage was held constant during electrodeposition using an Autolab Potentiostat. In all experiments, less than 0.5 % of the Mo was deposited, which insures that the plating reservoir remains at an approximately constant isotopic composition. Plated Mo was then recovered in acid, and the isotopic composition of samples and stock solutions were measured using a Thermo Scientific Neptune MC-ICP-MS. These experiments show that the redox process induces an isotopic signature with respect to the starting material, with a trend showing that fractionation decreases as a function of applied voltage.

  18. Prediction of new thermodynamically stable aluminum oxides

    PubMed Central

    Liu, Yue; Oganov, Artem R.; Wang, Shengnan; Zhu, Qiang; Dong, Xiao; Kresse, Georg

    2015-01-01

    Recently, it has been shown that under pressure, unexpected and counterintuitive chemical compounds become stable. Laser shock experiments (A. Rode, unpublished) on alumina (Al2O3) have shown non-equilibrium decomposition of alumina with the formation of free Al and a mysterious transparent phase. Inspired by these observations, we have explored the possibility of the formation of new chemical compounds in the system Al-O. Using the variable-composition structure prediction algorithm USPEX, in addition to the well-known Al2O3, we have found two extraordinary compounds Al4O7 and AlO2 to be thermodynamically stable in the pressure ranges 330-443?GPa and above 332?GPa, respectively. Both of these compounds at the same time contain oxide O2? and peroxide O22? ions, and both are insulating. Peroxo-groups are responsible for gap states, which significantly reduce the electronic band gap of both Al4O7 and AlO2. PMID:25830780

  19. Stable magnesium peroxide at high pressure.

    PubMed

    Lobanov, Sergey S; Zhu, Qiang; Holtgrewe, Nicholas; Prescher, Clemens; Prakapenka, Vitali B; Oganov, Artem R; Goncharov, Alexander F

    2015-01-01

    Rocky planets are thought to comprise compounds of Mg and O as these are among the most abundant elements, but knowledge of their stable phases may be incomplete. MgO is known to be remarkably stable to very high pressure and chemically inert under reduced condition of the Earth's lower mantle. However, in exoplanets oxygen may be a more abundant constituent. Here, using synchrotron x-ray diffraction in laser-heated diamond anvil cells, we show that MgO and oxygen react at pressures above 96 GPa and T = 2150 K with the formation of I4/mcm MgO2. Raman spectroscopy detects the presence of a peroxide ion (O2(2-)) in the synthesized material as well as in the recovered specimen. Likewise, energy-dispersive x-ray spectroscopy confirms that the recovered sample has higher oxygen content than pure MgO. Our finding suggests that MgO2 may be present together or instead of MgO in rocky mantles and rocky planetary cores under highly oxidized conditions. PMID:26323635

  20. Stable Lithium Argon compounds under high pressure

    PubMed Central

    Li, Xiaofeng; Hermann, Andreas; Peng, Feng; Lv, Jian; Wang, Yanchao; Wang, Hui; Ma, Yanming

    2015-01-01

    High pressure can fundamentally alter the bonding patterns of chemical elements. Its effects include stimulating elements thought to be “inactive” to form unexpectedly stable compounds with unusual chemical and physical properties. Here, using an unbiased structure search method based on CALYPSO methodology and density functional total energy calculations, the phase stabilities and crystal structures of Li?Ar compounds are systematically investigated at high pressure up to 300?GPa. Two unexpected LimArn compounds (LiAr and Li3Ar) are predicted to be stable above 112?GPa and 119?GPa, respectively. A detailed analysis of the electronic structure of LiAr and Li3Ar shows that Ar in these compounds attracts electrons and thus behaves as an oxidizing agent. This is markedly different from the hitherto established chemical reactivity of Ar. Moreover, we predict that the P4/mmm phase of Li3Ar has a superconducting transition temperature of 17.6?K at 120?GPa. PMID:26582083

  1. Stable Lithium Argon compounds under high pressure.

    PubMed

    Li, Xiaofeng; Hermann, Andreas; Peng, Feng; Lv, Jian; Wang, Yanchao; Wang, Hui; Ma, Yanming

    2015-01-01

    High pressure can fundamentally alter the bonding patterns of chemical elements. Its effects include stimulating elements thought to be "inactive" to form unexpectedly stable compounds with unusual chemical and physical properties. Here, using an unbiased structure search method based on CALYPSO methodology and density functional total energy calculations, the phase stabilities and crystal structures of Li-Ar compounds are systematically investigated at high pressure up to 300?GPa. Two unexpected LimArn compounds (LiAr and Li3Ar) are predicted to be stable above 112?GPa and 119?GPa, respectively. A detailed analysis of the electronic structure of LiAr and Li3Ar shows that Ar in these compounds attracts electrons and thus behaves as an oxidizing agent. This is markedly different from the hitherto established chemical reactivity of Ar. Moreover, we predict that the P4/mmm phase of Li3Ar has a superconducting transition temperature of 17.6?K at 120?GPa. PMID:26582083

  2. Color stable manganese-doped phosphors

    DOEpatents

    Lyons, Robert Joseph (Burnt Hills, NY); Setlur, Anant Achyut (Niskayuna, NY); Deshpande, Anirudha Rajendra (Twinsburg, OH); Grigorov, Ljudmil Slavchev (Sofia, BG)

    2012-08-28

    A process for preparing color stable Mn.sup.+4 doped phosphors includes providing a phosphor of formula I; A.sub.x[MF.sub.y]:Mn.sup.+4 I and contacting the phosphor in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid; A.sub.x[MF.sub.y]; II wherein A is Li, Na, K, Rb, Cs, NR.sub.4 or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; R is H, lower alkyl, or a combination thereof; x is the absolute value of the charge of the [MF.sub.y] ion; and y is 5, 6 or 7. In particular embodiments, M is Si, Ge, Sn, Ti, Zr, or a combination thereof. A lighting apparatus capable of emitting white light includes a semiconductor light source; and a phosphor composition radiationally coupled to the light source, and which includes a color stable Mn.sup.+4 doped phosphor.

  3. Stable magnesium peroxide at high pressure

    PubMed Central

    Lobanov, Sergey S.; Zhu, Qiang; Holtgrewe, Nicholas; Prescher, Clemens; Prakapenka, Vitali B.; Oganov, Artem R.; Goncharov, Alexander F.

    2015-01-01

    Rocky planets are thought to comprise compounds of Mg and O as these are among the most abundant elements, but knowledge of their stable phases may be incomplete. MgO is known to be remarkably stable to very high pressure and chemically inert under reduced condition of the Earth’s lower mantle. However, in exoplanets oxygen may be a more abundant constituent. Here, using synchrotron x-ray diffraction in laser-heated diamond anvil cells, we show that MgO and oxygen react at pressures above 96?GPa and T?=?2150?K with the formation of I4/mcm MgO2. Raman spectroscopy detects the presence of a peroxide ion (O22?) in the synthesized material as well as in the recovered specimen. Likewise, energy-dispersive x-ray spectroscopy confirms that the recovered sample has higher oxygen content than pure MgO. Our finding suggests that MgO2 may be present together or instead of MgO in rocky mantles and rocky planetary cores under highly oxidized conditions. PMID:26323635

  4. Stable Games Josef Hofbauer and William H. Sandholm

    E-print Network

    Hofbauer, Josef

    Stable Games Josef Hofbauer and William H. Sandholm Abstract-- We introduce a new class of population games called stable games. These games are characterized by self- defeating externalities: when are aban- doning. Stable games subsume many well-known classes of examples, including zero-sum games, games

  5. Incorporating uncertainty and prior information into stable isotope mixing models

    E-print Network

    LETTER Incorporating uncertainty and prior information into stable isotope mixing models Jonathan W@biology.ucsc.edu Authors contributed equally to this manuscript. Abstract Stable isotopes are a powerful tool). Mixing models use stable isotope data to estimate the contribution of sources to a mixture. Uncertainty

  6. Manipulation complexity and gender neutrality in stable marriage procedures

    E-print Network

    Rossi, Francesca

    Manipulation complexity and gender neutrality in stable marriage procedures Maria Silvia Pini1 to manipulate, we prove that there exist stable marriage procedures which are NP-hard to manipulate. We also which are NP-hard to manipulate can be used to define stable marriage procedures which are themselves NP

  7. Compact Preference Representation in Stable Marriage Enrico Pilotto1

    E-print Network

    Walsh, Toby

    Preference Representation in Stable Marriage Problems 391 gender. In addition, eliciting their preferencesCompact Preference Representation in Stable Marriage Problems Enrico Pilotto1 , Francesca Rossi1.Walsh@nicta.com.au Abstract. The stable marriage problem has many practical applications in two- sided markets like those

  8. A new proof of the stable manifold theorem

    NASA Astrophysics Data System (ADS)

    McGehee, Richard; Sander, Evelyn

    1996-07-01

    We give a new proof of the stable manifold theorem for hyperbolic fixed points of smooth maps. This proof shows that the local stable and unstable manifolds are projections of a relation obtained as a limit of the graphs of the iterates of the map. The same proof generalizes to the setting of stable and unstable manifolds for smooth relations.

  9. Test of Association Between Multivariate Stable Vectors \\Lambda

    E-print Network

    Rüschendorf, Ludger

    that the observations on the vector of returns are in the domain of attraction of a multivariate ff­stable law. While in the Domain of Attraction of (ff 1 ; \\Delta \\Delta \\Delta ; ff d )--stable laws 2.1 Association and Spectral vectors in the domain of attraction of a stable distribution with (multi­)index ff = (ff 1 ; \\Delta \\Delta

  10. Perceptual Learning Immediately Yields New Stable Motor Coordination

    ERIC Educational Resources Information Center

    Wilson, Andrew D.; Snapp-Childs, Winona; Bingham, Geoffrey P.

    2010-01-01

    Coordinated rhythmic movement is specifically structured in humans. Movement at 0[degrees] mean relative phase is maximally stable, 180[degrees] is less stable, and other coordinations can, but must, be learned. Variations in perceptual ability play a key role in determining the observed stabilities so we investigated whether stable movements can…

  11. IS SOLAR SYSTEM STABLE? Vladik Kreinovich, Andrew Bernat

    E-print Network

    Kreinovich, Vladik

    IS SOLAR SYSTEM STABLE? A REMARK Vladik Kreinovich, Andrew Bernat Computer Science Department System is stable or not. Common belief is that the Solar System is stable if and only that the Solar system does not have such resonances, and therefore (if the above­mentioned belief is correct), we

  12. IS SOLAR SYSTEM STABLE? Vladik Kreinovich, Andrew Bernat

    E-print Network

    Kreinovich, Vladik

    IS SOLAR SYSTEM STABLE? A REMARK Vladik Kreinovich, Andrew Bernat Computer Science Department System is stable or not. Common belief is that the Solar System is stable if and only, a similar inequality is true for randomly chosen frequencies. In this paper, we show that the Solar system

  13. Local search algorithms on the Stable Marriage Problem: Experimental Studies

    E-print Network

    Rossi, Francesca

    Local search algorithms on the Stable Marriage Problem: Experimental Studies M. Gelain, M. S. Pini, F. Rossi, K. B. Venable 1 and T. Walsh 2 Abstract. The stable marriage problem (SM) has a wide a stable marriage: a matching of men to women with no blocking pair. A blocking pair consists of a man

  14. Gale-Shapley Stable Marriage Problem Revisited: Strategic Issues

    E-print Network

    Sethuraman, Jay

    Gale-Shapley Stable Marriage Problem Revisited: Strategic Issues and Applications Chung-Piaw Teo@nus.edu.sg · jay@ieor.columbia.edu We study strategic issues in the Gale-Shapley stable marriage model behavior of the students need not be a major concern. (Stable Marriage; Strategic Issues; Gale

  15. Procedural Fairness in Stable Marriage Problems (Extended Abstract)

    E-print Network

    Rossi, Francesca

    Procedural Fairness in Stable Marriage Problems (Extended Abstract) Mirco Gelain University.walsh@nicta.com.au ABSTRACT The stable marriage problem is a well-known problem of matching men to women so that no man generally to any two-sided market. Given a stable marriage problem, it is possible to find a male

  16. Isotropic turbulence, stable layers: atmospheric fictions

    NASA Astrophysics Data System (ADS)

    Lovejoy, S.; Tuck, A.; Hovde, S.; Schertzer, D.

    2007-12-01

    Using state of the art drop sonde data (from 237 sondes over the Pacific) we examine two classical and fundamental idealizations of atmospheric science showing that they are untenable in the light of the vertical structure. The first is the notion of stable atmospheric layers. This is used for understanding atmospheric dynamics and thermodynamics, including notions such as potential vorticity. Using the drop sonde data, we show that each apparently stable layer is actually composed of a hierarchy of unstable layers themselves with embedded stable sublayers, each with unstable sub-sub layers etc. i.e. in a Russian doll-like fractal hierarchy whose dimension we estimate. We therefore argue that the notion is untenable and must be replaced by modern scaling notions. Although the same basic conclusion follows for conditional, dynamical and convective stability, we showed that their correlation exponent (quantifying their sparsenesses) were 0.36±0.056, 0.22±0.037, 0.15±0.016 respectively. The second idealization we examine is the turbulence assumption of isotropy. If we include intermittency, Kolmorogov's landmark proposal that fully developed turbulence has an "inertial subrange" with isotropic energy spectrum E(k) ? k**-? with ??5/3 has apparently been spectacularly confirmed in both the horizontal direction and in the time domain (k is a wavenumber). For gradients over a horizontal distance ?x this implies ?v??z**Hh (Hh=1/3 corresponds to ?=5/3; "<.>" indicates ensemble averaging). Remarkably, Hv for gradients over vertical distances ?z (?v??z**Hv) has not been seriously investigated. Using drop sonde data of horizontal wind, we find that from scales of 5 m to >10 km from the surface layer through to the top of the troposphere, Hv is close to (or larger) than the Bolgiano-Obukhov value 3/5. Hv>Hh implies that a) the atmosphere becomes progressively less stratified at smaller scales although in a scaling way; b) that at most a single (roughly) isotropic "sphero-scale" exists (often in the range 1- 100 cm).

  17. Stable strontium isotope fractionation in synthetic barite

    NASA Astrophysics Data System (ADS)

    Widanagamage, Inoka H.; Schauble, Edwin A.; Scher, Howie D.; Griffith, Elizabeth M.

    2014-12-01

    The mineral barite (BaSO4) accommodates strontium (Sr) in its crystal structure, providing an archive of Sr-isotopes (87Sr/86Sr and ?88/86Sr) in the highly stable sulfate mineral. We investigated mass dependent stable Sr-isotope fractionation (?88/86Sr = ?88/86Srsolid - ?88/86Srsolution) during inorganic precipitation of barite from a barium-rich solution by addition of sulfate under controlled conditions and compared this to equilibrium isotopic fractionation calculated using Density Functional Theory modeling. Sr-substituted barite is predicted to have lower 88Sr/86Sr than any other studied species, and at 25 °C will be about 0.6-0.7‰ lower than the two modeled Sr(H2O)82+-bearing salts that could approximate aqueous Sr2+. This agrees in direction and order of magnitude with experimental results that estimate equilibrium Sr-isotope fractionation in barite to be 0.3‰ lower than aqueous Sr2+ at ?20 °C. The high ionic strength of some of the precipitating solutions (up to 1 M) and potential differences in the average coordination number of aqueous Sr2+ add to uncertainty in a direct comparison of the calculated equilibrium isotopic fractionation values with the experimental results. Stable Sr-isotope fractionation varied along with the distribution coefficient of Sr [Kd(Sr) = [Sr/Ba]barite/[Sr/Ba]solution], which is a function of both temperature and barite saturation state. However the relationship between mass dependent isotopic fractionation and Kd(Sr) is different for conditions of changing temperature versus barite saturation state. With increasing temperature (from 5 to 40 °C), the barite phase became isotopically lighter (?88/86Sr = -0.29‰ to -0.41‰). Conversely, with increasing saturation state (saturation index of barite = 3.0-4.3) the barite phase became isotopically heavier (?88/86Sr = -0.25‰ to -0.10‰). These observations suggest chemical kinetic effects control isotopic fractionation rather than equilibrium temperature effects. The relationship with saturation state indicates the potential presence of a diffusive boundary layer. Barite crystal morphology appears to be affected by the diffusion rate of solute (sulfate) to the growing crystal surface relative to the overall growth rate of barite crystals during precipitation.

  18. Towards stable silicon nanoarray hybrid solar cells

    PubMed Central

    He, W. W.; Wu, K. J.; Wang, K.; Shi, T. F.; Wu, L.; Li, S. X.; Teng, D. Y.; Ye, C. H.

    2014-01-01

    Silicon nanoarray hybrid solar cells benefit from the ease of fabrication and the cost-effectiveness of the hybrid structure, and represent a new research focus towards the utilization of solar energy. However, hybrid solar cells composed of both inorganic and organic components suffer from the notorious stability issue, which has to be tackled before the hybrid solar cells could become a viable alternative for harvesting solar energy. Here we show that Si nanoarray/PEDOT:PSS hybrid solar cells with improved stability can be fabricated via eliminating the water inclusion in the initial formation of the heterojunction between Si nanoarray and PEDOT:PSS. The Si nanoarray hybrid solar cells are stable against rapid degradation in the atmosphere environment for several months without encapsulation. This finding paves the way towards the real-world applications of Si nanoarray hybrid solar cells. PMID:24430057

  19. Bounded excursion stable gravastars and black holes

    SciTech Connect

    Rocha, P; Da Silva, M F; Wang, Anzhong; Santos, N O E-mail: yasuda@on.br E-mail: mfasnic@gmail.com E-mail: anzhong_wang@baylor.edu

    2008-06-15

    Dynamical models of prototype gravastars were constructed in order to study their stability. The models are the Visser-Wiltshire three-layer gravastars, in which an infinitely thin spherical shell of stiff fluid divides the whole spacetime into two regions, where the internal region is de Sitter, and the external one is Schwarzschild. It is found that in some cases the models represent the 'bounded excursion' stable gravastars, where the thin shell is oscillating between two finite radii, while in other cases they collapse until the formation of black holes occurs. In the phase space, the region for the 'bounded excursion' gravastars is very small in comparison to that of black holes, but not empty. Therefore, although the possibility of the existence of gravastars cannot be excluded from such dynamical models, our results indicate that, even if gravastars do indeed exist, that does not exclude the possibility of the existence of black holes.

  20. Stable isotope investigations of chlorinated aliphatic hydrocarbons.

    SciTech Connect

    Abrajano, T.; Heraty, L. J.; Holt, B. D.; Huang, L.; Sturchio, N. C.

    1999-06-01

    Stable isotope ratio measurements for carbon (C) and chlorine (Cl) can be used to elucidate the processes affecting transformation and transportation of chlorinated aliphatic hydrocarbons (CAHs) in the environment. Methods recently developed in our laboratory for isotopic analysis of CAHs have been applied to laboratory measurements of the kinetic isotope effects associated with aerobic degradation of dichloromethane (DCM) and with both anaerobic and aerobic cometabolic degradation of trichlomethene (TCE) in batch and column microbial cultures. These experimental determinations of fractionation factors are crucial for understanding the behavior of CAHs in complex natural systems, where the extent of biotransformation can be masked by dispersion and volatilization. We have also performed laboratory investigations of kinetic isotope effects accompanying evaporation of CAHs, as well as field investigations of natural attenuation and in situ remediation of CAHs in a number of contaminated shallow aquifers at sites operated by the federal government and the private sector.

  1. Stable operating regime for traveling wave devices

    DOEpatents

    Carlsten, Bruce E. (Los Alamos, NM)

    2000-01-01

    Autophase stability is provided for a traveling wave device (TWD) electron beam for amplifying an RF electromagnetic wave in walls defining a waveguide for said electromagnetic wave. An off-axis electron beam is generated at a selected energy and has an energy noise inherently arising from electron gun. The off-axis electron beam is introduced into the waveguide. The off-axis electron beam is introduced into the waveguide at a second radius. The waveguide structure is designed to obtain a selected detuning of the electron beam. The off-axis electron beam has a velocity and the second radius to place the electron beam at a selected distance from the walls defining the waveguide, wherein changes in a density of the electron beam due to the RF electromagnetic wave are independent of the energy of the electron beam to provide a concomitant stable operating regime relative to the energy noise.

  2. Forces between stable non-BPS branes

    NASA Astrophysics Data System (ADS)

    Corley, Steven; Lowe, David A.

    2002-02-01

    As a step toward constructing realistic brane world models in string theory, we consider the interactions of a pair of non-BPS branes. We construct a dyonic generalization of the non-BPS branes first constructed by Bergman, Gaberdiel and Sen as orbifolds of D-branes on T4/Z2. The force between a dyonic brane and an electric brane is computed and is found to vanish at a non-trivial critical separation. This equilibrium point is unstable. For smaller separations the branes coalesce to form a composite dyonic state, while for larger separations the branes run off to infinity. We suggest generalizations that will lead to potentials with stable local minima.

  3. Stable quarks of the 4th family?

    E-print Network

    Belotsky, K; Shibaev, K

    2008-01-01

    Existence of metastable quarks of new generation can be embedded into phenomenology of heterotic string together with new long range interaction, which only this new generation possesses. We discuss primordial quark production in the early Universe, their successive cosmological evolution and astrophysical effects, as well as possible production in present or future accelerators. In case of a charge symmetry of 4th generation quarks in Universe, they can be stored in neutral mesons, doubly positively charged baryons, while all the doubly negatively charged "baryons" are combined with He-4 into neutral nucleus-size atom-like states. The existence of all these anomalous stable particles may escape present experimental limits, being close to present and future experimental test. Due to the nuclear binding with He-4 primordial lightest baryons of the 4th generation with charge +1 can also escape the experimental upper limits on anomalous isotopes of hydrogen, being compatible with upper limits on anomalous lithiu...

  4. Transient growth in stable collisionless plasma

    SciTech Connect

    Camporeale, Enrico; Burgess, David; Passot, Thierry

    2009-03-15

    The first kinetic study of transient growth for a collisionless homogeneous Maxwellian plasma in a uniform magnetic field is presented. A system which is linearly stable may display transient growth if the linear operator describing its evolution is non-normal so that its eigenvectors are nonorthogonal. In order to include plasma kinetic effects, a Landau fluid model is employed. The linear operator of the model is shown to be non-normal and the results suggest that the non-normality of a collisionless plasma is intrinsically related to its kinetic nature, with the transient growth being more accentuated for smaller scales and higher plasma beta. The results based on linear spectral theory have been confirmed with nonlinear simulations.

  5. Quantum isoperiodic stable structures and directed transport.

    PubMed

    Carlo, Gabriel G

    2012-05-25

    It has been recently found that the so-called isoperiodic stable structures (ISSs) have a fundamental role in the classical current behavior of dissipative ratchets [Phys. Rev. Lett. 106, 234101 (2011).]. Here I analyze their quantum counterparts, the quantum ISSs (QISSs), which have a fundamental role in the quantum current behavior. QISSs have the simple attractor shape of those ISSs which settle down in short times. However, in the majority of the cases they are strongly different from the ISSs, looking approximately the same as the quantum chaotic attractors that are at their vicinity in parameter space. By adding thermal fluctuations of the size of ?(eff) to the ISSs I am able to obtain very good approximations to the QISSs. I conjecture that in general, quantum chaotic attractors could be well approximated by means of just the classical information of a neighboring ISS plus thermal fluctuations. I expect to find this behavior in quantum dissipative systems in general. PMID:23003233

  6. Highly selective biaryl cross-coupling reactions between aryl halides and aryl Grignard reagents: a new catalyst combination of N-heterocyclic carbenes and iron, cobalt, and nickel fluorides.

    PubMed

    Hatakeyama, Takuji; Hashimoto, Sigma; Ishizuka, Kentaro; Nakamura, Masaharu

    2009-08-26

    Combinations of N-heterocyclic carbenes (NHCs) and fluoride salts of the iron-group metals (Fe, Co, and Ni) have been shown to be excellent catalysts for the cross-coupling reactions of aryl Grignard reagents (Ar(1)MgBr) with aryl and heteroaryl halides (Ar(2)X) to give unsymmetrical biaryls (Ar(1)-Ar(2)). Iron fluorides in combination with SIPr, a saturated NHC ligand, catalyze the biaryl cross-coupling between various aryl chlorides and aryl Grignard reagents in high yield and high selectivity. On the other hand, cobalt and nickel fluorides in combination with IPr, an unsaturated NHC ligand, exhibit interesting complementary reactivity in the coupling of aryl bromides or iodides; in contrast, with these substrates the iron catalysts show a lower selectivity. The formation of homocoupling byproducts is suppressed markedly to less than 5% in most cases by choosing the appropriate metal fluoride/NHC combination. The present catalyst combinations offer several synthetic advantages over existing methods: practical synthesis of a broad range of unsymmetrical biaryls without the use of palladium catalysts and phosphine ligands. On the basis of stoichiometric control experiments and theoretical studies, the origin of the unique catalytic effect of the fluoride counterion can be ascribed to the formation of a higher-valent heteroleptic metalate [Ar(1)MF(2)]MgBr as the key intermediate in our proposed catalytic cycle. First, stoichiometric control experiments revealed the stark differences in chemical reactivity between the metal fluorides and metal chlorides. Second, DFT calculations indicate that the initial reduction of di- or trivalent metal fluoride in the wake of transmetalation with PhMgCl is energetically unfavorable and that formation of a divalent heteroleptic metalate complex, [PhMF(2)]MgCl (M = Fe, Co, Ni), is dominant in the metal fluoride system. The heteroleptic ate-complex serves as a key reactive intermediate, which undergoes oxidative addition with PhCl and releases the biaryl cross-coupling product Ph-Ph with reasonable energy barriers. The present cross-coupling reaction catalyzed by iron-group metal fluorides and an NHC ligand provides a highly selective and practical method for the synthesis of unsymmetrical biaryls as well as the opportunity to gain new mechanistic insights into the metal-catalyzed cross-coupling reactions. PMID:19639999

  7. Stable quarks of the 4th family?

    E-print Network

    K. Belotsky; M. Khlopov; K. Shibaev

    2008-06-05

    Existence of metastable quarks of new generation can be embedded into phenomenology of heterotic string together with new long range interaction, which only this new generation possesses. We discuss primordial quark production in the early Universe, their successive cosmological evolution and astrophysical effects, as well as possible production in present or future accelerators. In case of a charge symmetry of 4th generation quarks in Universe, they can be stored in neutral mesons, doubly positively charged baryons, while all the doubly negatively charged "baryons" are combined with He-4 into neutral nucleus-size atom-like states. The existence of all these anomalous stable particles may escape present experimental limits, being close to present and future experimental test. Due to the nuclear binding with He-4 primordial lightest baryons of the 4th generation with charge +1 can also escape the experimental upper limits on anomalous isotopes of hydrogen, being compatible with upper limits on anomalous lithium. While 4th quark hadrons are rare, their presence may be nearly detectable in cosmic rays, muon and neutrino fluxes and cosmic electromagnetic spectra. In case of charge asymmetry, a nontrivial solution for the problem of dark matter (DM) can be provided by excessive (meta)stable anti-up quarks of 4th generation, bound with He-4 in specific nuclear-interacting form of dark matter. Such candidate to DM is surprisingly close to Warm Dark Matter by its role in large scale structure formation. It catalyzes primordial heavy element production in Big Bang Nucleosynthesis and new types of nuclear transformations around us.

  8. Deciphering Ecohydrological Interactions Using Stable Isotopes

    NASA Astrophysics Data System (ADS)

    McDonnell, J.; Evaristo, J. A.; Jasechko, S.

    2014-12-01

    Deciphering the nature of ecohydrological interconnections and scaling that knowledge gained at single points to watersheds is challenging. One tool that that has proved useful in this regard is stable isotope tracing. Single isotope studies have been used recently to quantify landuse change effects on streamflow source apportionment and ecological effects on transit time distributions of water at the catchment scale. However, most work to date has assumed that plant transpiration, groundwater recharge and streamflow are all sourced or mediated by the same well mixed reservoir—the soil. Recent work in Oregon and Mexico has shown evidence of ecohydrological separation, whereby different subsurface compartmentalized pools of water supply either plant transpiration fluxes or the combined fluxes of groundwater recharge and streamflow. However, these findings have not yet been widely tested. Here we assemble the first dual isotope database for ?2H and ?18O extracted from 47 globally-distributed stable isotopic datasets. We use these data to test the ecohydrological separation hypothesis. We combine this dual isotope dataset with global precipitation, streamwater, groundwater and soil water datasets. Our results show that precipitation, streamwater and groundwater from the 47 sites plot approximately along the ?2H/?18O slope of eight, suggesting that local precipitation inputs supply streamwater and groundwater. Soil waters extracted from the 47 studies plot below the regression of local streamwater and groundwater with a slope of 6.6±0.05 ‰. Local plant xylem waters from our matched dataset plot on a slope 6.6±0.07 ‰ consistent with local soil waters. The tight association of soil water slopes and not that of local groundwater or streamflow suggests that plants use soil water that does not itself contribute to groundwater recharge or stream water. This ubiquity of subsurface water compartmentalization is surprising and has important implications for how we conceptualize ecohydrological interactions in changing environments.

  9. Tungsten Stable Isotope Compositions of Ferromanganese Crusts

    NASA Astrophysics Data System (ADS)

    Abraham, K.; Barling, J.; Hein, J. R.; Schauble, E. A.; Halliday, A. N.

    2014-12-01

    We report the first accurate and precise data for mass-dependent fractionation of tungsten (W) stable isotopes, using a double spike technique and MC-ICPMS. Results are expressed relative to the NIST 3136 W isotope standard as per mil deviations in 186W/184W (?186W). Although heavy element mass-dependent fractionations are expected to be small, Tl and U both display significant low temperature isotopic fractionations. Theoretical calculations indicate that W nuclear volume isotopic effects should be smaller than mass-dependent fractionations at low temperatures. Hydrogenetic ferromanganese (Fe-Mn) crusts precipitate directly from seawater and have been used as paleoceanographic recorders of temporal changes in seawater chemistry. Crusts are strongly enriched in W and other metals, and are a promising medium for exploring W isotopic variability. Tungsten has a relatively long residence time in seawater of ~61,000 years, mainly as the tungstate ion (WO42-). Water depth profiles show conservative behaviour. During adsorption on Fe-Mn crusts, W species form inner-sphere complexes in the hexavalent (W6+) state. The major host phase is thought to be Mn oxides and the lighter W isotope is expected to be absorbed preferentially. Surface scrapings of 13 globally distributed hydrogenetic Fe-Mn crusts display ?186W from -0.08 to -0.22‰ (±0.03‰, 2sd). A trend toward lighter W isotope composition exists with increasing water depth (~1500 to ~5200m) and W concentration. One hydrothermal Mn-oxide sample is anomalously light and Mn nodules are both heavy and light relative to Fe-Mn crusts. Tungsten speciation depends on concentration, pH, and time in solution and is not well understood because of the extremely slow kinetics of the reactions. In addition, speciation of aqueous and/or adsorbed species might be sensitive to pressure, showing similar thermodynamic stability but different effective volumes. Thus, W stable isotopes might be used as a water-depth barometer in marine environments; time-series in Fe-Mn crusts may show a heavier isotope composition in older crust layers due to the shallower water environments in the early history of the seamounts on which the crusts grow.

  10. Embryotoxicity of stable isotopes and use of stable isotopes in studies of teratogenetic mechanisms

    SciTech Connect

    Spielmann, H.; Nau, H.

    1986-07-01

    Experiments on teratogenic effects of stable isotopes from our own and other laboratories are evaluated. In the first series of investigations, the enrichment of the stable isotope /sup 13/C derived from U-/sup 13/C-glucose was studied in mouse embryos at various stages of development, including limb buds in organ culture. Preimplantation mouse embryos incubated in vitro in /sup 13/C-enriched medium for 48 hours showed normal development during subsequent differentiation in vitro and also in vivo after embryo transfer to faster mothers. These embryos were 15% to 20% enriched in /sup 13/C. Administration of U-13-C-glucose to pregnant mice during organogenesis led to an increase of the absolute /sup 13/C content of the embryo for several days after the end of isotope administration, whereas the enrichment in maternal tissue decreased. No alterations of embryonic development were detected due to stable isotope enrichment. Development of cultured mouse limb buds was unaffected by incubation with 82 mol% U-/sup 13/C-glucose as judged from morphologic and biochemical criteria. The second part of the article describes the value of deuterium-labeled drugs as probes into the mechanism of activation of teratogenic metabolites. A comparison of the pharmacokinetics as well as the teratogenicity between cyclophosphamide and some specific deuterium-labeled analogues showed that the isotope effect observed can be related to a particular metabolic pathway crucial for teratogenic activation by this drug.

  11. Diamond Formation: A Stable Isotope Perspective

    NASA Astrophysics Data System (ADS)

    Cartigny, Pierre; Palot, Médéric; Thomassot, Emilie; Harris, Jeff W.

    2014-05-01

    Primarily on the basis of C, N, S, and O stable isotope systematics, this article reviews recent achievements in understanding diamond formation and growth in Earth's mantle. Diamond is a metasomatic mineral that results from either the reduction or oxidation of mobile C-bearing liquids (fluids or melts) that intrude preexisting lithologies (eclogites, peridotites, and metamorphic rocks). This process seems ubiquitous, as it occurs over a large range of depths and extends through time. Diamond-forming carbon derives mainly from the convective asthenosphere. Most of its isotopic anomalies reflect fractionation processes in the lithospheric mantle, which are attributed to diamond precipitation itself and/or a mineralogical control occurring prior to diamond precipitation. Evidence for a mineralogical control would be the decoupling of the 15N/14N ratios in eclogitic diamond from other tracers of subduction in inclusions in the same diamond. C isotope anomalies related to subduction are rare and are probably best seen in diamonds from the transition zone.

  12. The stable K0 giant star ? Gem

    SciTech Connect

    Gray, David F.

    2014-12-01

    A nine-season spectroscopic study of the photosphere of ? Gem (K0 III) shows this low-luminosity giant to be stable, with no effective temperature variations above ?2 K, and no secular temperature variations over the 2002-2010 time span above 0.2 K per year. The radial-velocity variations are consistent with an orbital variation of ?40 m s{sup –1}. The projected rotation rate is found to be 1.70 ± 0.20 km s{sup –1} with a macroturbulence dispersion of 4.53 ± 0.10 km s{sup –1}. The third-signature plot is also invariant and shows a granulation velocity gradient 20% smaller than the solar gradient. The absolute shift of the third-signature plot gives a blueshift-corrected radial velocity of 3385 ± 70 m s{sup –1}. Bisector mapping of the Fe I ?6253 line yields a flux deficit of 12% ± 1% in area, somewhat smaller than for other giants, but the shape and the position of the peak at 4.8 km s{sup –1} is consistent with other giants. All of the investigated photospheric parameters are consistent with ? Gem being a low-luminosity giant in agreement with its absolute magnitude.

  13. Stable Isotope Database: present and past archives

    NASA Astrophysics Data System (ADS)

    Bolliet, Timothé

    2014-05-01

    Paleoclimate data provide benchmarks against which the realism of the processes simulated by climate models can be assessed. Within this framework, it is essential to avoid introducing uncertainties associated with transfer functions and therefore to operate with robust proxies. The implementation of stable isotopes of water or carbon inside climate models motivates a synthesis of available data. Supported by the LABEX L-IPSL and involving a team of climate modelers and paleoclimatologists, this project aims to establish a worldwide database of ?18O, ?D ?17O and ?13C from oceanic microfossils, corals, ice cores, cave speleothems, lakes, tree rings, and vegetation leaves wax. The aim is to provide a global vision of the hydrological cycle during the LGM and other selected key periods (last 2000 years, Mid-Holocene, Dansgaard-Oeschger events, and the Eemian). It requires screening through hundreds of published oceanic and continental records, validating the selection of the data based on resolution and chronological information. We extracted ~900 dated ?18O records from 650 marine sediment cores, 65 ?18O records from 50 ice cores, ~200 ?18O speleothems records from 60 caves, and 540 ?13C records from 290 marine sediment cores. An additional aspect of this project consists in the construction of an online portal providing an intuitive and interactive platform allowing selecting, visualizing, and downloading of the records included in this database, thus improving the distribution and comparison of paleoclimatic records from various sites.

  14. How structurally stable are global socioeconomic systems?

    PubMed Central

    Saavedra, Serguei; Rohr, Rudolf P.; Gilarranz, Luis J.; Bascompte, Jordi

    2014-01-01

    The stability analysis of socioeconomic systems has been centred on answering whether small perturbations when a system is in a given quantitative state will push the system permanently to a different quantitative state. However, typically the quantitative state of socioeconomic systems is subject to constant change. Therefore, a key stability question that has been under-investigated is how strongly the conditions of a system itself can change before the system moves to a qualitatively different behaviour, i.e. how structurally stable the systems is. Here, we introduce a framework to investigate the structural stability of socioeconomic systems formed by a network of interactions among agents competing for resources. We measure the structural stability of the system as the range of conditions in the distribution and availability of resources compatible with the qualitative behaviour in which all the constituent agents can be self-sustained across time. To illustrate our framework, we study an empirical representation of the global socioeconomic system formed by countries sharing and competing for multinational companies used as proxy for resources. We demonstrate that the structural stability of the system is inversely associated with the level of competition and the level of heterogeneity in the distribution of resources. Importantly, we show that the qualitative behaviour of the observed global socioeconomic system is highly sensitive to changes in the distribution of resources. We believe that this work provides a methodological basis to develop sustainable strategies for socioeconomic systems subject to constantly changing conditions. PMID:25165600

  15. The Stable K0 Giant Star ? Gem

    NASA Astrophysics Data System (ADS)

    Gray, David F.

    2014-12-01

    A nine-season spectroscopic study of the photosphere of ? Gem (K0 III) shows this low-luminosity giant to be stable, with no effective temperature variations above ~2 K, and no secular temperature variations over the 2002-2010 time span above 0.2 K per year. The radial-velocity variations are consistent with an orbital variation of ~40 m s-1. The projected rotation rate is found to be 1.70 ± 0.20 km s-1 with a macroturbulence dispersion of 4.53 ± 0.10 km s-1. The third-signature plot is also invariant and shows a granulation velocity gradient 20% smaller than the solar gradient. The absolute shift of the third-signature plot gives a blueshift-corrected radial velocity of 3385 ± 70 m s-1. Bisector mapping of the Fe I ?6253 line yields a flux deficit of 12% ± 1% in area, somewhat smaller than for other giants, but the shape and the position of the peak at 4.8 km s-1 is consistent with other giants. All of the investigated photospheric parameters are consistent with ? Gem being a low-luminosity giant in agreement with its absolute magnitude.

  16. Exotic stable cesium polynitrides at high pressure

    PubMed Central

    Peng, Feng; Han, Yunxia; Liu, Hanyu; Yao, Yansun

    2015-01-01

    New polynitrides containing metastable forms of nitrogen are actively investigated as potential high-energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50?GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3, N4, N5, N6) and chains (N?). Polymeric chains of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44? anion. To our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure. PMID:26581175

  17. Three new stable L5 Mars Trojans

    NASA Astrophysics Data System (ADS)

    de la Fuente Marcos, C.; de la Fuente Marcos, R.

    2013-05-01

    Mars was second to Jupiter in being recognized as the host of a population of Trojan minor bodies. Since 1990, five asteroids - 5261 Eureka, (101429) 1998 VF31, (121514) 1999 UJ7, 2001 DH47 and (311999) 2007 NS2 - have been identified as Mars Trojans, one L4 and four L5. Dynamical and spectroscopic evidence suggests that some Mars Trojans may be remnants of the original planetesimal population that formed in the terrestrial planets region. Here, we revisit the long-term dynamical evolution of the previously known Mars Trojans and show that 2011 SC191, 2011 SL25 and 2011 UN63 are also trailing (L5) Mars Trojans. They appear to be as stable as Eureka and may have been Trojans over the age of the Solar system. The fact that five Trojans move in similar orbits and one of them is a binary may point to the disruption of a larger body early in the history of the Solar system. Such a catastrophic event may also explain the apparently strong asymmetry in terms of number of objects (one versus seven) between the L4 and L5 regions. Future spectroscopic observations should be able to reject or confirm a putative common chemical signature that may lend further support to a collisional scenario.

  18. Exotic stable cesium polynitrides at high pressure

    NASA Astrophysics Data System (ADS)

    Peng, Feng; Han, Yunxia; Liu, Hanyu; Yao, Yansun

    2015-11-01

    New polynitrides containing metastable forms of nitrogen are actively investigated as potential high-energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50?GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3, N4, N5, N6) and chains (N?). Polymeric chains of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44? anion. To our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure.

  19. Directional flow sensing by passively stable larvae.

    PubMed

    Fuchs, Heidi L; Christman, Adam J; Gerbi, Gregory P; Hunter, Elias J; Diez, F Javier

    2015-09-01

    Mollusk larvae have a stable, velum-up orientation that may influence how they sense and react to hydrodynamic signals applied in different directions. Directional sensing abilities and responses could affect how a larva interacts with anisotropic fluid motions, including those in feeding currents and in boundary layers encountered during settlement. Oyster larvae (Crassostrea virginica) were exposed to simple shear in a Couette device and to solid-body rotation in a single rotating cylinder. Both devices were operated in two different orientations, one with the axis of rotation parallel to the gravity vector, and one with the axis perpendicular. Larvae and flow were observed simultaneously with near-infrared particle-image velocimetry, and behavior was quantified as a response to strain rate, vorticity and centripetal acceleration. Only flows rotating about a horizontal axis elicited the diving response observed previously for oyster larvae in turbulence. The results provide strong evidence that the turbulence-sensing mechanism relies on gravity-detecting organs (statocysts) rather than mechanosensors (cilia). Flow sensing with statocysts sets oyster larvae apart from zooplankters such as copepods and protists that use external mechanosensors in sensing spatial velocity gradients generated by prey or predators. Sensing flow-induced changes in orientation, rather than flow deformation, would enable more efficient control of vertical movements. Statocysts provide larvae with a mechanism of maintaining their upward swimming when rotated by vortices and initiating dives toward the seabed in response to the strong turbulence associated with adult habitats. PMID:26333930

  20. Color stable manganese-doped phosphors

    DOEpatents

    Lyons, Robert Joseph; Setlur, Anant Achyut; Deshpande, Anirundha Rajendra; Grigorov, Ljudmil Slavchev

    2014-04-29

    A lighting apparatus capable of emitting white light includes a semiconductor light source; and a phosphor material radiationally coupled to the light source. The phosphor material includes a color-stable Mn.sup.+4 doped phosphor prepared by a process including providing a phosphor of formula I; A.sub.x[MF.sub.y]:Mn.sup.+4 I and contacting the phosphor in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid; A.sub.x[MF.sub.y]; II wherein A is Li, Na, K, Rb, Cs, NR.sub.4 or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; R is H, lower alkyl, or a combination thereof; x is the absolute value of the charge of the [MF.sub.y] ion; and y is 5, 6 or 7. In particular embodiments, M is Si, Ge, Sn, Ti, Zr, or a combination thereof.

  1. Exotic stable cesium polynitrides at high pressure.

    PubMed

    Peng, Feng; Han, Yunxia; Liu, Hanyu; Yao, Yansun

    2015-01-01

    New polynitrides containing metastable forms of nitrogen are actively investigated as potential high-energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50?GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3, N4, N5, N6) and chains (N?). Polymeric chains of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N4(4-) anion. To our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure. PMID:26581175

  2. Learning Stable Multilevel Dictionaries for Sparse Representations.

    PubMed

    Thiagarajan, Jayaraman J; Ramamurthy, Karthikeyan Natesan; Spanias, Andreas

    2015-09-01

    Sparse representations using learned dictionaries are being increasingly used with success in several data processing and machine learning applications. The increasing need for learning sparse models in large-scale applications motivates the development of efficient, robust, and provably good dictionary learning algorithms. Algorithmic stability and generalizability are desirable characteristics for dictionary learning algorithms that aim to build global dictionaries, which can efficiently model any test data similar to the training samples. In this paper, we propose an algorithm to learn dictionaries for sparse representations from large scale data, and prove that the proposed learning algorithm is stable and generalizable asymptotically. The algorithm employs a 1-D subspace clustering procedure, the K-hyperline clustering, to learn a hierarchical dictionary with multiple levels. We also propose an information-theoretic scheme to estimate the number of atoms needed in each level of learning and develop an ensemble approach to learn robust dictionaries. Using the proposed dictionaries, the sparse code for novel test data can be computed using a low-complexity pursuit procedure. We demonstrate the stability and generalization characteristics of the proposed algorithm using simulations. We also evaluate the utility of the multilevel dictionaries in compressed recovery and subspace learning applications. PMID:25343771

  3. HUNT STABLE COMPLEX LOOKING NORTHWEST TOWARD DOG KENNEL RUINS ACROSS ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    HUNT STABLE COMPLEX LOOKING NORTHWEST TOWARD DOG KENNEL RUINS ACROSS THE GREAT CIRCUS - Overhills, Fort Bragg Military Reservation, Approximately 15 miles NW of Fayetteville, Overhills, Harnett County, NC

  4. Stable Vanadium Isotope Fractionation at High Temperatures

    NASA Astrophysics Data System (ADS)

    Prytulak, J.; Parkinson, I. J.; Savage, P. S.; Nielsen, S. G.; Halliday, A. N.

    2011-12-01

    Vanadium is a redox sensitive transition metal existing in multiple valence states at terrestrial conditions. Stable vanadium isotopes (reported as ?51V in % relative to an Alfa Aesar standard [1]) are a potentially powerful tracer of oxidation-reduction processes. However, the determination of ?51V is analytically challenging, primarily due to the extreme abundance ratio between the only two stable isotopes (51V/50V ~ 400) and, also, significant isobaric interferences of 50Ti and 50Cr on the minor 50V isotope. We have developed the first method able to determine ?51V to a precision (2 s.d. ~ 0.15%, [1,2]) that enables application of this isotope system to geological processes. To usefully investigate high temperature processes using vanadium isotopes, knowledge of the isotope composition and range of values present in the ambient mantle is required. Here we discuss the first ?51V measured in igneous materials encompassing peridotites, MORB, and primitive mantle-derived melts such as picrites. This first dataset provides a preliminary reconnaissance of the magnitude of natural fractionation. We find little isotope fractionation in suites of peridotites and MORB (< 0.5 %). However, the small but analytically significant variation appears to be related to secondary processes, with extremely altered peridotites consistently displaying slightly heavier isotope compositions. We find no resolvable ?51V variation between fresh MORB glass and fresh peridotite. Intriguingly, a suite of subduction-related peridotites from the Mariana forearc, previously characterized for fO2 [3], do not display the predicted co-variation between ?51V and fO2, but instead also have compositions identical to MORB glass. This nominally supports recent indications that there is limited difference in the oxygen fugacity of the MORB source and the subarc mantle wedge [e.g., 4, 5]. Finally, we observe large ?51V variations (~ 2 %) in a suite of evolving lavas from Hekla volcano, Iceland, which produces eruptive material with a wide range of SiO2 from a cogenetic source. The ?51V of Hekla lavas are well correlated with indices of differentiation such as MgO and SiO2, suggesting that processes such as fractional crystallization may be a fundamental cause of high temperature ?51V fractionation. This nascent dataset provides a first glimpse into the magnitude of vanadium isotope fractionation that may be expected at high temperatures. The presence of significant isotope variation outside of analytical precision in these materials bodes well for the use of ?51V to address a variety of broad scale questions in high temperature planetary processes. [1] Nielsen, S.G., Prytulak, J., Halliday, A.N. 2011. Geost. Geoanal. Res., in press. [2] Prytulak, J., Nielsen, S.G., Halliday, A.N. 2011. Geost. Geoanal. Res., in press. [3] Parkinson and Pearce, 1998. Journal of Petrology, 39, 1577-1618. [4] Lee et al., 2005. Journal of Petrology, 46, 2313-2336. [5] Cottrell and Kelley, 2011. Earth and Planetary Sciences Letters, 305, 270-282.

  5. Shelf-stable electrophilic reagents for trifluoromethylthiolation.

    PubMed

    Shao, Xinxin; Xu, Chunfa; Lu, Long; Shen, Qilong

    2015-05-19

    Fluorine, which is the most electronegative element and has a small atomic radius, plays a key role in pharmaceutical, agrochemical, and materials sciences. One of the fluoroalkyl groups, the trifluoromethylthio group (CF3S-), has been well-recognized as an important structural motif in the design of lead compounds for new drug discovery because of its high lipophilicity (Hansch lipophilicity parameter ? = 1.44) and strong electron-withdrawing properties, which could improve the drug molecule's cell-membrane permeability and enhance its chemical and metabolic stability. While classic methods for the preparation of trifluoromethylthiolated compounds typically involve halogen-fluorine exchange reactions of polyhalogenomethyl thioethers or trifluoromethylation of sulfur-containing compounds under harsh reaction conditions, an alternative but more attractive strategy is direct trifluoromethylthiolation of the substrate at a late stage by employing an electrophilic trifluoromethylthiolating reagent. Although several electrophilic trifluoromethylthiolating reagents have been reported previously, these reagents either require a strong Lewis acid/Brønsted acid as an activator or suffer from a toxic nature or limited substrate scope. To address these problems, in late 2011 we initiated a project with the aim to develop new, shelf-stable, and highly reactive electrophilic trifluoromethylthiolating reagents that could easily install the trifluoromethylthio group at the desired positions of the drug molecule at a late stage of drug development. Inspired by the broad reactivity of the hypervalent iodine reagent, we initially discovered a highly reactive trifluoromethylthiolating reagent, trifluoromethanesulfenate 1a. Structure-reactivity studies disclosed that the iodine atom of reagent 1a does not play an important role in this reagent's reactivity. Consequently, a simplified second-generation electrophilic reagent, trifluoromethanesulfenate 1b, was developed. In parallel, we developed another shelf-stable, highly reactive electrophilic reagent with a broad substrate scope, N-trifluoromethylthiosaccharin (2). In this Account, we mainly describe our discovery of these two different types of electrophilic trifluoromethylthiolating reagents, trifluoromethanesulfenates 1a and 1b and N-trifluoromethylthiosaccharin 2. Systematic studies showed that both types of reagents are highly reactive toward a wide range of nucleophiles, yet the substrate scopes of these two different types of reagents are complementary. In particular, reagents 1a and 1b are more reliable in transition-metal-catalyzed reactions such as copper-catalyzed trifluoromethylthiolation of aryl/vinyl/alkylboronic acids and silver-catalyzed decarboxylative trifluoromethylthiolation of aliphatic carboxylic acids as well as in the organocatalytic asymmetric trifluoromethylthiolation of ?-keto esters and oxindoles. Reagent 2 is more electrophilic than reagents 1a and 1b and is more efficient for direct trifluoromethylthiolation with nucleophiles such as alcohols, amines, thiols, and electron-rich arenes. The ease in preparation, broad scope, and mild reaction conditions make reagents 1a, 1b, and 2 very attractive as general reagents that allow rapid installation of the trifluoromethylthio group into small molecules. PMID:25947041

  6. Stable Isotope Applications in Hydrologic Studies

    NASA Astrophysics Data System (ADS)

    Kendall, C.; Doctor, D. H.

    2003-12-01

    The topic of stream flow generation has received considerable attention over the last two decades, first in response to concern about "acid rain" and more recently in response to the increasingly serious contamination of surface and shallow groundwaters by anthropogenic contaminants. Many sensitive, low-alkalinity streams in North America and Europe are already acidified (see Chapter 9.10). Still more streams that are not yet chronically acidic may undergo acidic episodes in response to large rainstorms and/or spring snowmelt. These acidic events can seriously damage local ecosystems. Future climate changes may exacerbate the situation by affecting biogeochemical controls on the transport of water, nutrients, and other materials from land to freshwater ecosystems.New awareness of the potential danger to water supplies posed by the use of agricultural chemicals and urban industrial development has also focused attention on the nature of rainfall-runoff and recharge processes and the mobility of various solutes, especially nitrate and pesticides, in shallow systems. Dumping and spills of other potentially toxic materials are also of concern because these chemicals may eventually reach streams and other public water supplies. A better understanding of hydrologic flow paths and solute sources is required to determine the potential impact of contaminants on water supplies, develop management practices to preserve water quality, and devise remediation plans for sites that are already polluted.Isotope tracers have been extremely useful in providing new insights into hydrologic processes, because they integrate small-scale variability to give an effective indication of catchment-scale processes. The main purpose of this chapter is to provide an overview of recent research into the use of naturally occurring stable isotopes to track the movement of water and solutes in hydrological systems where the waters are relatively fresh: soils, surface waters, and shallow groundwaters. For more information on shallow-system applications, the reader is referred to Kendall and McDonnell (1998). For information on groundwater systems, see Cook and Herczeg (2000).

  7. NATURAL STABLE CARBON ISOTOPE TAG TRACES TEXAS SHRIMP MIGRATIONSl

    E-print Network

    NATURAL STABLE CARBON ISOTOPE TAG TRACES TEXAS SHRIMP MIGRATIONSl BRIAN FRy2 ABSTRACf A 1978 spring and early summer survey of Texas brown shrimp, Penaeus aztecus, showed that stable carbon isotope t13 C/12 C or 1l'3C) analysis is useful for tracing shrimp movements. At least four isotopi- cally distinct shrimp

  8. Manipulation and gender neutrality in stable marriage Maria Silvia Pini

    E-print Network

    Rossi, Francesca

    Manipulation and gender neutrality in stable marriage procedures Maria Silvia Pini Univ. of Padova be manipulated. Whilst the Gale-Shapley algorithm is computationally easy to manipulate, we prove-hard to manipulate can be used to define stable marriage procedures which are themselves NP-hard to manipulate

  9. STABLE MODELS AND REFLEXIVE BANACH SPACES JOSE IOVINO

    E-print Network

    Iovino, José - Iovino, José

    STABLE MODELS AND REFLEXIVE BANACH SPACES JOS´E IOVINO ABSTRACT. We show that a formula (x, y) is stable if and only if is the pairing map on the unit ball of E � E, where E is a reflexive Banach space. A similar distinction exists in Banach space geometry between reflexive and nonre- flexive spaces. A Banach

  10. Tracing Increasing Tropical Andean Glacier Melt with Stable Isotopes in

    E-print Network

    McKenzie, Jeffrey M.

    Tracing Increasing Tropical Andean Glacier Melt with Stable Isotopes in Water B R Y A N G . M A R K short-term increases in discharge as glaciers melt and demonstrate the utility of stable isotopes in water for tracing relative glacier melt water contributions to watersheds. Introduction The future

  11. Homogeneous Epidemic Systems in the Stable Hisashi Inaba

    E-print Network

    Inaba, Hisashi

    Homogeneous Epidemic Systems in the Stable Population Hisashi Inaba Department of Mathematical Sciences, University of Tokyo, 3-8-1 Komaba Meguro-ku, Tokyo 153-8914 Japan E-mail: inaba that the host population dynamics is described by the stable population model, we rewrite the basic system

  12. Communications Formation of a Stable Dihydrido(alkyl)platinum(IV)

    E-print Network

    Keinan, Ehud

    Communications Formation of a Stable Dihydrido(alkyl)platinum(IV) Complex by Water Activation Ariel-stable dihydrido- (methyl)platinum(IV) complex TpPtH2Me (1; Tp ) hy- dridotris(pyrazolyl)borate) is formed followed by protonation at the platinum center to produce 1. The direct, selective oxidation of alkanes has

  13. 12. VIEW OF THE SOUTHWEST ELEVATION OF THE STABLES. THE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    12. VIEW OF THE SOUTHWEST ELEVATION OF THE STABLES. THE STABLES ARE LOCATED AT THE EXTREME SOUTHWESTERN END OF THE MINE COMPLEX. - Tower Hill No. 2 Mine, Approximately 0.47 mile Southwest of intersection of Stone Church Road & Township Route 561, Hibbs, Fayette County, PA

  14. A TRIPTYCH OF DISCRETE DISTRIBUTIONS RELATED TO THE STABLE LAW

    E-print Network

    Devroye, Luc

    A TRIPTYCH OF DISCRETE DISTRIBUTIONS RELATED TO THE STABLE LAW Luc Devroye School of Computer uniformly fast random variate generators. Keywords and phrases. Discrete stable distribution. Random variate05. Authors' address: School of Computer Science, McGill University, 3480 University Street, Montreal

  15. ECOPHYSIOLOGY Determining biological tissue turnover using stable isotopes

    E-print Network

    Ehleringer, Jim

    ECOPHYSIOLOGY Determining biological tissue turnover using stable isotopes: the reaction progress variable is applied to stable isotope turnover of biological tissues. This ap- proach has the advantage of readily determining whe- ther more than one isotope turnover pool is present; in addition

  16. Stable Receding Horizon Trajectory Control for Complex Environments

    E-print Network

    a stable receding horizon con- troller for the minimum time trajectory optimization problem with a vehicle an input trajectory that optimizes the plant's output over a period of time, called the planning horizonStable Receding Horizon Trajectory Control for Complex Environments John Bellingham , Yoshiaki

  17. Compressive Sensing for Ultrasound RF Echoes Using -Stable Distributions

    E-print Network

    Tsakalides, Panagiotis

    Compressive Sensing for Ultrasound RF Echoes Using -Stable Distributions Alin Achim, Benjamin for compressive sensing of biomedical ultrasonic signals based on modelling data with stable distributions. We. In this paper, we propose to exploit the fairly new theory of compressive sensing (CS) [1], [2] to provide

  18. Enhanced trapping of stable flies via olfactory and visual cues

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Adult stable flies are highly attracted to the so-called Alsynite cylinder trap; however this trap is expensive. Here we report the development of a cheaper and better white panel trap with options of adding visual and olfactory stimuli for enhanced stable fly trapping. The white panel trap attracte...

  19. Use of stable isotope analysis in determining aquatic food webs

    EPA Science Inventory

    Stable isotope analysis is a useful tool for describing resource-consumer dynamics in ecosystems. In general, organisms of a given trophic level or functional feeding group will have a stable isotope ratio identifiable different than their prey because of preferential use of one ...

  20. STABLE STATE OF INTERCONNECT UNDER TEMPERATURE CHANGE AND ELECTRIC CURRENT

    E-print Network

    Suo, Zhigang

    STABLE STATE OF INTERCONNECT UNDER TEMPERATURE CHANGE AND ELECTRIC CURRENT Z. SUO Mechanical electric current, such an interconnect evolvesÐafter a compli- cated sequence of eventsÐinto a stable state, and no further mass diusion. The electric current continues in the shunt layers where aluminum is depleted

  1. Stable Carbon Isotope Fractionation during Aerobic Biodegradation of

    E-print Network

    Chu, Kung-Hui "Bella"

    Stable Carbon Isotope Fractionation during Aerobic Biodegradation of Chlorinated Ethenes K U N G and Caldwell, 201 North Civic Drive, Walnut Creek, California 94596, and Center for Isotope Geochemistry, MS 70A-4418, Lawrence Berkeley National Laboratory, Berkeley, California 94720 Stable isotope analysis

  2. Compact preference representation in stable marriage E. Pilotto1

    E-print Network

    Rossi, Francesca

    Compact preference representation in stable marriage problems E. Pilotto1 , F. Rossi1 , K. B.Walsh@nicta.com.au Abstract. The stable marriage problem has many practical applications in two- sided markets like those marriages assume that the par- ticipants explicitly expresses a preference ordering. This can be problematic

  3. Tail Bounds for the Stable Marriage of Poisson and Lebesgue

    E-print Network

    Holroyd, Alexander

    Tail Bounds for the Stable Marriage of Poisson and Lebesgue Christopher Ho#man # , Alexander E of the Gale­Shapley marriage problem. We study the distance X from a typical site to its allocated center (USA) grants DMS­0104073 and DMS­0244479 and by MSRI and CPAM Key words: stable marriage, point process

  4. Stable Isotope Fractionation of Metallic Elements

    NASA Astrophysics Data System (ADS)

    Albarede, F.

    2001-12-01

    The 70s and the 80s saw the demonstration that some anomalous isotope compositions in planetary material are inherited from heterogeneities in the Solar Nebula and that some others reflect spallation induced by strong radiation events. In addition, a variety of mass-independent fractionation processes were shown to affect the isotopic composition of atmospheric O, C, and S. In the mean time, the patterns of mass-dependent fractionation of most elements, notably metals, remained largely ignored, presumably because the state-of-the-art precision of existing analytical techniques (mostly double-spike) was inadequate. The debate largely focused on why no isotopic fractionation could actually be observed, e.g., for K and Fe in planetary objects, within the limits of the current analytical uncertainties (0.1 to 1~‰ ). The advent of multiple-collector ICP MS suddenly improved the precision on isotopic measurements to a typical 40 ppm on elements such as Cu, Zn, Fe, Mg, Mo, etc. The ongoing exploration of the stable isotope geochemistry of metallic elements is revealing that their natural isotopic variability is much more widespread and stronger than previously anticipated, typically 1~‰ for Zn and Fe to 10~‰ for Cu. The mechanisms of isotopic fractionation that create this variability remain to be determined. The bulk of Zn and Fe in planetary material is apparently derived from an isotopically homogeneous source. The first data on meteorites reveal, however, that the isotopic heterogeneities of Cu and Zn in planetary objects correlate with 16O excess. Redox reactions cannot be the deus-ex-machina of the isotope geochemistry of metals: isotope fractionation in ores and soils is far more ubiquitous and far stronger for Cu than for Fe. Cu fractionation by ion exchange in solution is much stronger for chloride complexes than for free ions in nitric solutions. Volatilization processes also need to be better understood: the Zn isotope variability of iron meteorites is nearly an order of magnitude larger than that of the rest of planetary material altogether regardless of its apparent volatile element depletion. A careful investigation of the coordination and of molecular symmetry in vapor, aqueous solutions, solids and liquid metals is a pre-requisite to the understanding of these newly discovered isotopic effects.

  5. On fractional tempered stable processes and their governing differential equations

    NASA Astrophysics Data System (ADS)

    Beghin, Luisa

    2015-07-01

    We derive the governing equation of the Tempered Stable Subordinator (hereafter TSS), which generalizes the space-fractional differential equation satisfied by the law of the ?-stable subordinator itself. This equation is expressed in terms of the shifted fractional derivative of order ? ? (0 , 1) coinciding with the stability parameter. We then generalize this equation by introducing a time-fractional derivative of order ? ? (0 , 1) (resp. 1 / ? > 1) and we prove that it is satisfied by the law of a TSS time-changed by the inverse of a ?-stable subordinator (resp. by the stable subordinator itself). The corresponding processes can therefore be called "fractional TS processes". Finally we provide fractional extensions of the relativistic stable processes, which we define as a Brownian motion with a random time argument represented by independent fractional TS processes of order ? (resp. 1 / ?).

  6. Stable mammalian producer cell lines for structural biology.

    PubMed

    Büssow, Konrad

    2015-06-01

    The mammalian cell lines HEK293 and CHO have become important expression hosts in structural biology. Generating stable mammalian cell lines remains essential for studying the function and structure of recombinant proteins, despite the emergence of highly efficient transient transfection protocols. Production with stable cell lines can be scaled up easily and high volumetric product yield can be achieved. Protein structure reports of the past two years that used stable cell lines were surveyed for this review. Well-established techniques and novel approaches for generating stable cell lines and stable cell pools are presented, including cell sorting, site-specific recombination, transposons, the Lentivirus system and phage integrases. Host cell line optimization by endoglycosidase overexpression and sequence-specific genome engineering is highlighted. PMID:25804355

  7. Negative tension branes as stable thin shell wormholes

    NASA Astrophysics Data System (ADS)

    Kokubu, Takafumi; Harada, Tomohiro

    2015-10-01

    We investigate negative tension branes as stable thin shell wormholes (TSWs) in Reissner-Nordström-(anti) de Sitter spacetimes in d dimensional Einstein gravity. Imposing Z2 symmetry, we construct and classify traversable static TSWs in spherical, planar (or cylindrical) and hyperbolic symmetries. In spherical geometry, we find the higher dimensional counterpart of Barceló and Visser’s wormholes, which are stable against spherically symmetric perturbations. We also find the classes of TSWs in planar and hyperbolic symmetries with a negative cosmological constant, which are stable against perturbations preserving symmetries. In most cases, stable wormholes are found with the combination of an electric charge and a negative cosmological constant. However, as special cases, we find stable wormholes even with vanishing cosmological constant in spherical symmetry and with vanishing electric charge in hyperbolic symmetry.

  8. Compact, Highly Stable Ion Atomic Clock

    NASA Technical Reports Server (NTRS)

    Prestage, John

    2008-01-01

    A mercury-ion clock now at the breadboard stage of development (see figure) has a stability comparable to that of a hydrogen-maser clock: In tests, the clock exhibited an Allan deviation of between 2 x 10(exp -13) and 3 x 10(exp -13) at a measurement time of 1 second, averaging to about 10(exp -15) at 1 day. However, the clock occupies a volume of only about 2 liters . about a hundredth of the volume of a hydrogen-maser clock. The ion-handling parts of the apparatus are housed in a sealed vacuum tube, wherein only a getter pump is used to maintain the vacuum. Hence, this apparatus is a prototype of a generation of small, potentially portable high-precision clocks for diverse ground- and space-based navigation and radio science applications. Furthermore, this new ion-clock technology is about 100 times more stable and precise than the rubidium atomic clocks currently in use in the NAV STAR GPS Earth-orbiting satellites. In this clock, mercury ions are shuttled between a quadrupole and a 16-pole linear radio-frequency trap. In the quadrupole trap, the ions are tightly confined and optical state selection from a Hg-202 radio-frequency-discharge ultraviolet lamp is carried out. In the 16-pole trap, the ions are more loosely confined and atomic transitions resonant at frequency of about 40.507 GHz are interrogated by use of a microwave beam at that frequency. The trapping of ions effectively eliminates the frequency pulling caused by wall collisions inherent to gas-cell clocks. The shuttling of the ions between the two traps enables separation of the state-selection process from the clock microwave- resonance process, so that each of these processes can be optimized independently of the other. The basic ion-shuttling, two-trap scheme as described thus far is not new: it has been the basis of designs of prior larger clocks. The novelty of the present development lies in major redesigns of its physics package (the ion traps and the vacuum and optical subsystems) to effect the desired reduction of size to a volume of no more than a couple of liters. The redesign effort has included selection of materials for the vacuum tube, ion trap, and ultraviolet windows that withstand bakeout at a temperature of approx.450 C in preparation for sealing the tube to contain the vacuum. This part of the redesign effort follows the approach taken in the development of such other vacuum-tube electronic components as flight traveling- wave-tube amplifiers having operational and shelf lives as long as 15 years. The redesign effort has also included a thorough study of residual-gas-induced shifts of the ion-clock frequency and a study of alternative gases as candidates for use as a buffer gas within the sealed tube. It has been found that neon is more suitable than is helium, which has been traditionally used for this purpose, in that the pressure-induced frequency pulling by neon is between a third and a half of that of helium. In addition, because neon diffuses through solids much more slowly than does helium, the loss of neon by diffusion over the operational lifetime is expected to be negligible.

  9. High-Order Entropy Stable Formulations for Computational Fluid Dynamics

    NASA Technical Reports Server (NTRS)

    Carpenter, Mark H.; Fisher, Travis C.

    2013-01-01

    A systematic approach is presented for developing entropy stable (SS) formulations of any order for the Navier-Stokes equations. These SS formulations discretely conserve mass, momentum, energy and satisfy a mathematical entropy inequality. They are valid for smooth as well as discontinuous flows provided sufficient dissipation is added at shocks and discontinuities. Entropy stable formulations exist for all diagonal norm, summation-by-parts (SBP) operators, including all centered finite-difference operators, Legendre collocation finite-element operators, and certain finite-volume operators. Examples are presented using various entropy stable formulations that demonstrate the current state-of-the-art of these schemes.

  10. Environmental and biomedical applications of natural metal stable isotope variations

    USGS Publications Warehouse

    Bullen, T.D.; Walczyk, T.

    2009-01-01

    etal stable isotopes are now being used to trace metal contaminants in the environment and as indicators of human systemic function where metals play a role. Stable isotope abundance variations provide information about metal sources and the processes affecting metals in complex natural systems, complementing information gained from surrogate tracers, such as metal abundance ratios or biochemical markers of metal metabolism. The science is still in its infancy, but the results of initial studies confirm that metal stable isotopes can provide a powerful tool for forensic and biomedical investigations.

  11. N-heterocyclic carbene catalysis: expansion of 

    E-print Network

    Ogle, James William

    2009-05-15

    in certain positions, for example as 1,3-dialkylated species (thus, the elaboration of the final chiral center in Lardolure using stoichiometric chiral sulfone auxiliary, Scheme 1.3, steps d-g). Low temperatures (-78 o C) are also required for high.... g Exactly 1:1 d.r. from the racemic substrate, ee of the diastereomers was 57% and 52% respectively. h Only 22% conversion was obtained with this substrate. entry substrate product ee (%) a a OH OH b 83 b OTBS OTBS c 49 c O b,e OH 54 d...

  12. Robust multiuser detection in ?-stable distribution non-Gaussian noise 

    E-print Network

    Zhang, Jing

    2002-01-01

    In this thesis, we will model the ambient non-Gaussian noise as the ?-stable distribution because this model has many attractive properties. By using this noise model, the robust multiuser detectors achieve significant performance gain, and the two...

  13. Interspecific Competition & Stable Coexistence Competition Resource-Limited Growth

    E-print Network

    Caraco, Thomas

    Interspecific Competition & Stable Coexistence Competition Resource-Limited Growth Outcomes: Interspecific Competition 1. Competitive Exclusion: One Species Extinct BioDiversity Lost 2. Competitive Species Effects on Population Growth Candidates for Competitive Coexistence Weakly Connected Species, Each

  14. Carbon stable isotopes suggest that hippopotamus-vectored nutrients subsidize

    E-print Network

    Lewison, Rebecca

    Carbon stable isotopes suggest that hippopotamus-vectored nutrients subsidize aquatic consumers that hippopotamus-vectored nutrients subsidize aquatic consumers in an East African river. Ecosphere 6(4):52. http

  15. Stable isotope views on ecosystem function: challenging or challenged?

    PubMed Central

    Resco, Víctor; Querejeta, José I.; Ogle, Kiona; Voltas, Jordi; Sebastià, Maria-Teresa; Serrano-Ortiz, Penélope; Linares, Juan C.; Moreno-Gutiérrez, Cristina; Herrero, Asier; Carreira, José A.; Torres-Cañabate, Patricia; Valladares, Fernando

    2010-01-01

    Stable isotopes and their potential for detecting various and complex ecosystem processes are attracting an increasing number of scientists. Progress is challenging, particularly under global change scenarios, but some established views have been challenged. The IX meeting of the Spanish Association of Terrestrial Ecology (AAET, Úbeda, 18–22 October 2009) hosted a symposium on the ecology of stable isotopes where the linear mixing model approach of partitioning sinks and sources of carbon and water fluxes within an ecosystem was challenged, and new applications of stable isotopes for the study of plant interactions were evaluated. Discussion was also centred on the need for networks that monitor ecological processes using stable isotopes and key ideas for fostering future research with isotopes. PMID:20015858

  16. 9 CFR 108.10 - Outer premises and stables.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ...108.10 Section 108.10 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT...premises. (b) Stables or other premises for animals used in the production or testing of biological products at licensed...

  17. 9 CFR 108.10 - Outer premises and stables.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ...108.10 Section 108.10 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT...premises. (b) Stables or other premises for animals used in the production or testing of biological products at licensed...

  18. 9 CFR 108.10 - Outer premises and stables.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ...108.10 Section 108.10 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT...premises. (b) Stables or other premises for animals used in the production or testing of biological products at licensed...

  19. 9 CFR 108.10 - Outer premises and stables.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ...108.10 Section 108.10 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT...premises. (b) Stables or other premises for animals used in the production or testing of biological products at licensed...

  20. 9 CFR 108.10 - Outer premises and stables.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ...108.10 Section 108.10 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT...premises. (b) Stables or other premises for animals used in the production or testing of biological products at licensed...

  1. Temperature Compensated Sapphire Resonator for Ultra-Stable Oscillator Capability

    NASA Technical Reports Server (NTRS)

    Dick, G. J.; Santiago, D. G.; Wang, R. T.

    1994-01-01

    We report on the design and test of a whispering gallery sapphire resonator for which the dominant microwave mode family shows frequency-stable, compensated operation for temperatures above 77 kelvin.

  2. 1. BACKSIDE OF FOUNDRY FROM NORTH LOOKING SOUTHWEST. STABLES CARRIAGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. BACKSIDE OF FOUNDRY FROM NORTH LOOKING SOUTHWEST. STABLES CARRIAGE HOUSE ON RIGHT, COKE STORAGE YARD MIDDLE GROUND, FOUNDRY BACKGROUND. - Knight Foundry, 13 Eureka Street, Sutter Creek, Amador County, CA

  3. Dark Atoms of Dark Matter and their Stable Charged Constituents

    E-print Network

    Maxim Yu. Khlopov

    2011-11-11

    Direct searches for dark matter lead to serious problems for simple models with stable neutral Weakly Interacting Massive Particles (WIMPs) as candidates for dark matter. A possibility is discussed that new stable quarks and charged leptons exist and are hidden from detection, being bound in neutral dark atoms of composite dark matter. Stable -2 charged particles $O^{--}$ are bound with primordial helium in O-helium (OHe) atoms, being specific nuclear interacting form of composite dark matter. The positive results of DAMA experiments can be explained as annual modulation of radiative capture of O-helium by nuclei. In the framework of this approach test of DAMA results in detectors with other chemical content becomes a nontrivial task, while the experimental search of stable charged particles at LHC or in cosmic rays acquires a meaning of direct test for composite dark matter scenario.

  4. Stable isotope labeling strategy based on coding theory.

    PubMed

    Kasai, Takuma; Koshiba, Seizo; Yokoyama, Jun; Kigawa, Takanori

    2015-10-01

    We describe a strategy for stable isotope-aided protein nuclear magnetic resonance (NMR) analysis, called stable isotope encoding. The basic idea of this strategy is that amino-acid selective labeling can be considered as "encoding and decoding" processes, in which the information of amino acid type is encoded by the stable isotope labeling ratio of the corresponding residue and it is decoded by analyzing NMR spectra. According to the idea, the strategy can diminish the required number of labelled samples by increasing information content per sample, enabling discrimination of 19 kinds of non-proline amino acids with only three labeled samples. The idea also enables this strategy to combine with information technologies, such as error detection by check digit, to improve the robustness of analyses with low quality data. Stable isotope encoding will facilitate NMR analyses of proteins under non-ideal conditions, such as those in large complex systems, with low-solubility, and in living cells. PMID:26293126

  5. On the genealogy of conditioned stable Levy forests.

    E-print Network

    On the genealogy of conditioned stable L´evy forests. June 25, 2007 L. Chaumont1 and J.C. Pardo2 and the contour process whose definition is recalled here in section 2. Both processes describe the genealogical

  6. A new intermediate for the production of flexible stable polymers

    NASA Technical Reports Server (NTRS)

    Webster, J. A.

    1973-01-01

    Method of incorporating ether linkages into perfluoroalkylene segment of a dianydride intermediate yields intermediate that may be used in synthesis of flexible, stable polyimides for use as high-temperature, solvent-resistant sealants.

  7. Statistically stable ultrasonic imaging in random media James G. Berryman

    E-print Network

    Papanicolaou, George C.

    Statistically stable ultrasonic imaging in random media James G. Berryman University of California processing, random media I. INTRODUCTION Imaging in ultrasonics is closely related to recent studies of time

  8. BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

    EPA Science Inventory

    The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

  9. 13. VIEW OF THE GABLE FRONT OF THE STABLES, LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    13. VIEW OF THE GABLE FRONT OF THE STABLES, LOOKING NORTHWEST. - Tower Hill No. 2 Mine, Approximately 0.47 mile Southwest of intersection of Stone Church Road & Township Route 561, Hibbs, Fayette County, PA

  10. 1. GENERAL VIEW (This building was originally a stable for ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. GENERAL VIEW (This building was originally a stable for the Patrick Calhoun House at 16 Meeting Street. It was later converted into a house.) - Patrick Calhoun House, 19 Church Street, Charleston, Charleston County, SC

  11. Massive stable charged particle signatures in simulations at the LHC

    E-print Network

    Silva, James B. (James Brian)

    2008-01-01

    The importance of heavy stable charged (HSCP) particles lies in the exploration of extensions to the standard model. Extensions of the standard model attempt to solve current problems in the standard model such as the ...

  12. Stable Recovery of Sparse Signals and an Oracle Inequality

    E-print Network

    Cai, T. Tony

    This article considers sparse signal recovery in the presence of noise. A mutual incoherence condition which was previously used for exact recovery in the noiseless case is shown to be sufficient for stable recovery in the ...

  13. Understanding stable levitation of superconductors from intermediate electromagnetics

    E-print Network

    Majós, Antonio Badía

    . INTRODUCTION Levitation experiments based on the repulsion (or attraction) force between permanent magnets universities are equipped with a magnetic levitation kit. Almost everyone is amused and stimulatedUnderstanding stable levitation of superconductors from intermediate electromagnetics A. Bad

  14. GENERAL VIEW OF ADOBE STABLES, WITH MISCELLANEOUS OUTBUILDINGS TO LEFT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    GENERAL VIEW OF ADOBE STABLES, WITH MISCELLANEOUS OUTBUILDINGS TO LEFT (WEST) AND TO RIGHT NEAR SWIMMING POOL (EAST); CAMERA FACING NORTHEAST - Harry Carey Ranch, 28515 San Francisquito Canyon Road, Saugus, Los Angeles County, CA

  15. Speed of light as measured by two terrestrial stable clocks

    NASA Technical Reports Server (NTRS)

    Hsu, J. P.; Sherry, T. N.; Chiu, C. B.

    1977-01-01

    Despite the recent criticism within the special theory of relativity, there exists an arrangement of stable clocks rotating with the earth which predicts diurnal variations of the one-way speed of light, as suggested previously.

  16. Ultra-Stable Oscillators for Probe Radio Science Investigations

    NASA Technical Reports Server (NTRS)

    Asmar, Sami

    2012-01-01

    An Ultra-Stable Oscillator (USO) is: A frequency reference, and A clock It is stable, small, and sensitive. It is a science and an art form. It is flown on spacecraft/probes. It]is utilized at ground stations alone or as a cleanup loop. It eliminates lock-up time on uplink for occultation egress & effect of media on uplink signal. It has enabled significant planetary science investigations.

  17. Entropy stable schemes for initial-boundary-value conservation laws

    NASA Astrophysics Data System (ADS)

    Svärd, Magnus; Mishra, Siddhartha

    2012-12-01

    We consider initial-boundary-value problems for systems of conservation laws and design entropy stable finite difference schemes to approximate them. The schemes are shown to be entropy stable for a large class of systems that are equipped with a symmetric splitting, derived from the entropy formulation. Numerical examples for the Euler equations of gas dynamics are presented to illustrate the robust performance of the proposed method.

  18. Chlorine stable isotopes in sedimentary systems: does size matter?

    NASA Technical Reports Server (NTRS)

    Coleman, Max

    2004-01-01

    Stable isotope abundances vary because of size differences. The chlorine stable isotope system was one of the first described theoretically, but had a slow, disappointment strewn development, relative to other elements. Method improvement gave only small, but significant, differences in compositions of geological materials. Eventually, brines and groundwater chlorides gave larger differences. Physical processes like diffusion and adsorption, probably are the main controls of groundwater compositions. Recent work on anthropogenic groundwater contaminants shows variations resulting from manufacturing processes; implying possibilities of tracing sources.

  19. Classification of structures in the stable boundary layer

    NASA Astrophysics Data System (ADS)

    Belusic, Danijel

    2015-04-01

    Ubiquitous but generally unknown flow structures populate the stable boundary layer at scales larger than turbulence. They introduce nonstationarity, affect the generation of turbulence and induce fluxes. Classification of the structures into clusters based on a similarity measure could reduce their apparent complexity and lead to better understanding of their characteristics and mechanisms. Here we explore different approaches to detect and classify structures, the usefulness of those approaches, and their potential to provide better understanding of the stable boundary layer.

  20. 7. OVERALL VIEW OF ROOM 110 (STABLES), LOOKING EAST. THE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    7. OVERALL VIEW OF ROOM 110 (STABLES), LOOKING EAST. THE LONG, LOW SPACE IS DIVIDED INTO AISLES BY EXPOSED POSTS AND BEAMS; POSTS ARE PAINTED. CEILING TREATMENT CHANGES FROM GYPSUM BOARD TO WOOD PLANKS IN THE CENTER AISLE. THE CONCRETE SLAB FLOOR IS SLOPED FROM CENTER FOR DRAINAGE PURPOSES. SMALL, HIGH WINDOWS LINE THE NORTHEAST AND SOUTHWEST WALLS. - Presidio of San Francisco, Cavalry Stables, Cowles Street, between Lincoln Boulevard & McDowell Street, San Francisco, San Francisco County, CA

  1. Generalization of symmetric ?-stable Lévy distributions for q>1

    PubMed Central

    Umarov, Sabir; Tsallis, Constantino; Gell-Mann, Murray; Steinberg, Stanly

    2010-01-01

    The ?-stable distributions introduced by Lévy play an important role in probabilistic theoretical studies and their various applications, e.g., in statistical physics, life sciences, and economics. In the present paper we study sequences of long-range dependent random variables whose distributions have asymptotic power-law decay, and which are called (q,?)-stable distributions. These sequences are generalizations of independent and identically distributed ?-stable distributions and have not been previously studied. Long-range dependent (q,?)-stable distributions might arise in the description of anomalous processes in nonextensive statistical mechanics, cell biology, finance. The parameter q controls dependence. If q=1 then they are classical independent and identically distributed with ?-stable Lévy distributions. In the present paper we establish basic properties of (q,?)-stable distributions and generalize the result of Umarov et al. [Milan J. Math. 76, 307 (2008)], where the particular case ?=2,q?[1,3) was considered, to the whole range of stability and nonextensivity parameters ??(0,2] and q?[1,3), respectively. We also discuss possible further extensions of the results that we obtain and formulate some conjectures. PMID:20596232

  2. Medieval Horse Stable; The Results of Multi Proxy Interdisciplinary Research

    PubMed Central

    Dejmal, Miroslav; Lisá, Lenka; Fišáková Nývltová, Miriam; Bajer, Aleš; Petr, Libor; Ko?ár, Petr; Ko?árová, Romana; Nejman, Ladislav; Rybní?ek, Michal; S?vová, Zdenka; Culp, Randy; Vavr?ík, Hanuš

    2014-01-01

    A multi proxy approach was applied in the reconstruction of the architecture of Medieval horse stable architecture, the maintenance practices associated with that structure as well as horse alimentation at the beginning of 13th century in Central Europe. Finally, an interpretation of the local vegetation structure along Morava River, Czech Republic is presented. The investigated stable experienced two construction phases. The infill was well preserved and its composition reflects maintenance practices. The uppermost part of the infill was composed of fresh stabling, which accumulated within a few months at the end of summer. Horses from different backgrounds were kept in the stable and this is reflected in the results of isotope analyses. Horses were fed meadow grasses as well as woody vegetation, millet, oat, and less commonly hemp, wheat and rye. Three possible explanations of stable usage are suggested. The stable was probably used on a temporary basis for horses of workers employed at the castle, courier horses and horses used in battle. PMID:24670874

  3. Manipulation and gender neutrality in stable marriage procedures

    E-print Network

    Pini, Maria; Venable, Brent; Walsh, Toby

    2009-01-01

    The stable marriage problem is a well-known problem of matching men to women so that no man and woman who are not married to each other both prefer each other. Such a problem has a wide variety of practical applications ranging from matching resident doctors to hospitals to matching students to schools. A well-known algorithm to solve this problem is the Gale-Shapley algorithm, which runs in polynomial time. It has been proven that stable marriage procedures can always be manipulated. Whilst the Gale-Shapley algorithm is computationally easy to manipulate, we prove that there exist stable marriage procedures which are NP-hard to manipulate. We also consider the relationship between voting theory and stable marriage procedures, showing that voting rules which are NP-hard to manipulate can be used to define stable marriage procedures which are themselves NP-hard to manipulate. Finally, we consider the issue that stable marriage procedures like Gale-Shapley favour one gender over the other, and we show how to us...

  4. Medieval horse stable; the results of multi proxy interdisciplinary research.

    PubMed

    Dejmal, Miroslav; Lisá, Lenka; Fišáková Nývltová, Miriam; Bajer, Aleš; Petr, Libor; Ko?ár, Petr; Ko?árová, Romana; Nejman, Ladislav; Rybní?ek, Michal; S?vová, Zdenka; Culp, Randy; Vavr?ík, Hanuš

    2014-01-01

    A multi proxy approach was applied in the reconstruction of the architecture of Medieval horse stable architecture, the maintenance practices associated with that structure as well as horse alimentation at the beginning of 13th century in Central Europe. Finally, an interpretation of the local vegetation structure along Morava River, Czech Republic is presented. The investigated stable experienced two construction phases. The infill was well preserved and its composition reflects maintenance practices. The uppermost part of the infill was composed of fresh stabling, which accumulated within a few months at the end of summer. Horses from different backgrounds were kept in the stable and this is reflected in the results of isotope analyses. Horses were fed meadow grasses as well as woody vegetation, millet, oat, and less commonly hemp, wheat and rye. Three possible explanations of stable usage are suggested. The stable was probably used on a temporary basis for horses of workers employed at the castle, courier horses and horses used in battle. PMID:24670874

  5. Metal stable isotope signatures as tracers in environmental geochemistry.

    PubMed

    Wiederhold, Jan G

    2015-03-01

    The biogeochemical cycling of metals in natural systems is often accompanied by stable isotope fractionation which can now be measured due to recent analytical advances. In consequence, a new research field has emerged over the last two decades, complementing the traditional stable isotope systems (H, C, O, N, S) with many more elements across the periodic table (Li, B, Mg, Si, Cl, Ca, Ti, V, Cr, Fe, Ni, Cu, Zn, Ge, Se, Br, Sr, Mo, Ag, Cd, Sn, Sb, Te, Ba, W, Pt, Hg, Tl, U) which are being explored and potentially applicable as novel geochemical tracers. This review presents the application of metal stable isotopes as source and process tracers in environmental studies, in particular by using mixing and Rayleigh model approaches. The most important concepts of mass-dependent and mass-independent metal stable isotope fractionation are introduced, and the extent of natural isotopic variations for different elements is compared. A particular focus lies on a discussion of processes (redox transformations, complexation, sorption, precipitation, dissolution, evaporation, diffusion, biological cycling) which are able to induce metal stable isotope fractionation in environmental systems. Additionally, the usefulness and limitations of metal stable isotope signatures as tracers in environmental geochemistry are discussed and future perspectives presented. PMID:25640608

  6. Study on stable and meta-stable carbides in a high speed steel for rollers during tempering processes

    NASA Astrophysics Data System (ADS)

    Guo, Jing; Qu, Hong-wei; Liu, Li-gang; Sun, Yan-liang; Zhang, Yue; Yang, Qing-xiang

    2013-02-01

    A high speed steel (HSS) was studied for rollers in this work. The steel was quenched at 1150°C and tempered at 520°C. The phase structures of the steel were determined by X-ray diffraction (XRD), and the hardness of specimens was measured. The volume fraction of carbides was counted by Image-Pro Plus software. The typical microstructures were observed by field emission scanning electron microscope (FESEM). Stable and meta-stable carbides were deduced by removing the existing phases one by one in the Fe-C equilibrium calculation. It is found that the precipitated carbides are bulk-like MC, long stripe-like M2C, fishbone-like M6C, and daisy-like M7C3 during the tempering process. The stable carbides are MC and M6C, but the meta-stable ones are M2C, M7C3, and M3C.

  7. Compound specific stable isotope analysis vs. bulk stable isotope analysis of agricultural food products

    NASA Astrophysics Data System (ADS)

    Psomiadis, David; Horváth, Balázs; Nehlich, Olaf; Bodiselitsch, Bernd

    2015-04-01

    The bulk analysis of stable isotopes (carbon, nitrogen, sulphur, oxygen and hydrogen) from food staples is a common tool for inferring origin and/or fraud of food products. Many studies have shown that bulk isotope analyses of agricultural products are able to separate large geographical areas of food origin. However, in micro-localities (regions, districts, and small ranges) these general applications fail in precision and discriminative power. The application of compound specific analysis of specific components of food products helps to increase the precision of established models. Compound groups like fatty acids (FAMEs), vitamins or amino acids can help to add further detailed information on physiological pathways and local conditions (micro-climate, soil, water availability) and therefore might add further information for the separation of micro-localities. In this study we are aiming to demonstrate the power and surplus of information of compound specific isotope analysis in comparison to bulk analysis of agricultural products (e.g. olive oil, cereal crops or similar products) and discuss the advantages and disadvantages of such (labor intense) analysis methods. Here we want to identify tools for further detailed analysis of specific compounds with high powers of region separation for better prediction models.

  8. Stable retrograde orbits around the triple system 2001 SN263

    NASA Astrophysics Data System (ADS)

    Araujo, R. A. N.; Winter, O. C.; Prado, A. F. B. A.

    2015-06-01

    The near-Earth Asteroid 2001 SN263 is a triple system of asteroids and it is the target of the ASTER mission - First Brazilian Deep Space Mission. The announcement of this mission has motivated a study aimed to characterize regions of stability of the system. Araujo et al., characterized the stable regions around the components of the triple system for the planar and prograde cases. Through numerical integrations they found that the stable regions are in two tiny internal zones, one of them placed very close to Alpha and another close to Beta, and in the external region. For a space mission aimed to place the probe in the internal region of the system those results do not seem to be very interesting. Therefore, knowing that the retrograde orbits are expected to be more stable, here we present a complementary study. We now considered particles orbiting the components of the system, in the internal and external regions, with relative inclinations between 90° < I ? 180°, i.e. particles with retrograde orbits. Our goal is to characterize the stable regions of the system for retrograde orbits, and then detach a preferred region to place the space probe. For a space mission, the most interesting regions would be those that are unstable for the prograde cases, but stable for the retrograde cases. Such configuration provide a stable region to place the mission probe with a relative retrograde orbit, and, at the same time, guarantees a region free of debris since they are expected to have prograde orbits. We found that in fact the internal and external stable regions significantly increase when compared to the prograde case. For particles with e = 0 and I = 180°, we found that nearly the whole region around Alpha and Beta remain stable. We then identified three internal regions and one external region that are very interesting to place the space probe. We present the stable regions found for the retrograde case and a discussion on those preferred regions. We also discuss the effects of resonances of the particles with Beta and Gamma, and the role of the Kozai mechanism in this scenario. These results help us understand and characterize the stability of the triple system 2001 SN263 when retrograde orbits are considered, and provide important parameters to the design of the ASTER mission.

  9. Molecular modeling of a stable glass -- the case of trehalose

    NASA Astrophysics Data System (ADS)

    Singh, Sadanand; Averett, Devin; de Pablo, Juan

    2010-03-01

    Recently, a new class of glasses --stable glasses- has been identified in experiments using physical vapor deposition of indometahcin (IMC) and 1,3,5-(tris)naphthylbenzene (TNB) [1,2]. These glasses have been shown to exhibit lower enthalpies (by as much as 10J/g), higher glass transition temperatures, higher onset temperature when subjected to plasticization and higher densities (by ˜2%) than traditional, ordinary glasses. We propose a molecular simulation method to generate stable glasses of an atomistic model of trehalose. The results of simulations are in good agreement with experiment: simulated stable trehalose glasses have an enthalpy that is 9.3 J/g lower and a density that is 1.6% than traditional, ordinary glasses. The plasticization of stable glasses formed by our method shows an increase of the onset temperature from 378K to 450K. Further analysis shows that these glasses have higher mechanical strength and higher Q6 crystal order parameter than ordinary glasses. The molecules farthest from the substrate layer are observed to be more mobile than those in the bulk; a mechanism for stable glass formation is proposed that relies on this enhanced surface mobility. [1] S. F. Swallenet al., Science. 2007, 315, 353-356, [2] K. L. Kearns et al., J Chem. Phys. 2007, 127.

  10. Development of stable influenza vaccine powder formulations: challenges and possibilities.

    PubMed

    Amorij, J-P; Huckriede, A; Wilschut, J; Frijlink, H W; Hinrichs, W L J

    2008-06-01

    Influenza vaccination represents the cornerstone of influenza prevention. However, today all influenza vaccines are formulated as liquids that are unstable at ambient temperatures and have to be stored and distributed under refrigeration. In order to stabilize influenza vaccines, they can be brought into the dry state using suitable excipients, stabilizers and drying processes. The resulting stable influenza vaccine powder is independent of cold-chain facilities. This can be attractive for the integration of the vaccine logistics with general drug distribution in Western as well as developing countries. In addition, a stockpile of stable vaccine formulations of potential vaccines against pandemic viruses can provide an immediate availability and simple distribution of vaccine in a pandemic outbreak. Finally, in the development of new needle-free dosage forms, dry and stable influenza vaccine powder formulations can facilitate new or improved targeting strategies for the vaccine compound. This review represents the current status of dry stable inactivated influenza vaccine development. Attention is given to the different influenza vaccine types (i.e. whole inactivated virus, split, subunit or virosomal vaccine), the rationale and need for stabilized influenza vaccines, drying methods by which influenza vaccines can be stabilized (i.e. lyophilization, spray drying, spray-freeze drying, vacuum drying or supercritical fluid drying), the current status of dry influenza vaccine development and the challenges for ultimate market introduction of a stable and effective dry-powder influenza vaccine. PMID:18338241

  11. Development of Stable Influenza Vaccine Powder Formulations: Challenges and Possibilities

    PubMed Central

    Amorij, J-P.; Huckriede, A.; Wilschut, J.; Frijlink, H. W.

    2008-01-01

    Influenza vaccination represents the cornerstone of influenza prevention. However, today all influenza vaccines are formulated as liquids that are unstable at ambient temperatures and have to be stored and distributed under refrigeration. In order to stabilize influenza vaccines, they can be brought into the dry state using suitable excipients, stabilizers and drying processes. The resulting stable influenza vaccine powder is independent of cold-chain facilities. This can be attractive for the integration of the vaccine logistics with general drug distribution in Western as well as developing countries. In addition, a stockpile of stable vaccine formulations of potential vaccines against pandemic viruses can provide an immediate availability and simple distribution of vaccine in a pandemic outbreak. Finally, in the development of new needle-free dosage forms, dry and stable influenza vaccine powder formulations can facilitate new or improved targeting strategies for the vaccine compound. This review represents the current status of dry stable inactivated influenza vaccine development. Attention is given to the different influenza vaccine types (i.e. whole inactivated virus, split, subunit or virosomal vaccine), the rationale and need for stabilized influenza vaccines, drying methods by which influenza vaccines can be stabilized (i.e. lyophilization, spray drying, spray-freeze drying, vacuum drying or supercritical fluid drying), the current status of dry influenza vaccine development and the challenges for ultimate market introduction of a stable and effective dry-powder influenza vaccine. PMID:18338241

  12. Stable Isotope Ratios and the Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Jarman, Kristin H.

    2007-06-01

    In the aftermath of the anthrax letters of 2001, researchers have been exploring various analytical signatures for the purpose of characterizing the production environment of microorganisms. One such signature is stable isotope ratios, which in heterotrophs are a function of nutrient and water sources. Here we discuss the use of stable isotope ratios in microbe forensics, using as a database the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of 247 separate cultures of B. subtilis 6051 spores produced on a total of 32 different culture media. In the context of using stable isotope ratios as a signature for sample matching, we present an analysis of variation between individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times. Additionally, we correlate the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen for growth medium nutrients or water with those of spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures.

  13. A TREETOPS Simulation of the STABLE Microgravity Vibration Isolation System

    NASA Technical Reports Server (NTRS)

    Nurre, G. S.; Whorton, M. S.; Kim, Y. K.

    1999-01-01

    As a research facility for microgravity science, the International Space Station (ISS) will be used for numerous experiments which require a quiescent acceleration environment across a broad spectrum of frequencies. For many micro-gravity science experiments, the ambient acceleration environment on ISS will significantly exceed desirable levels. The ubiquity of acceleration disturbance sources and the difficulty in characterization of these sources precludes source isolation, requiring, vibration isolation to attenuate the disturbances to an acceptable level at the experiment. To provide a more quiescent acceleration environment, a vibration isolation system named STABLE (Suppression of Transient Accelerations By LEvitation) was developed. STABLE was the first successful flight test of an active isolation device for micro-gravity science payloads and was flown on STS-73/USML-2 in October 1995. This report documents the development of the high fidelity, nonlinear, multibody simulation developed using TREETOPS which was used to design the control laws and define the expected performance of the STABLE isolation system.

  14. Stable Neutral Atom Trap with a Thin Superconducting Disc

    SciTech Connect

    Shimizu, Fujio; Hufnagel, Christoph; Mukai, Tetsuya

    2009-12-18

    A stable magnetic quadrupole trap for neutral atoms on a superconducting Nb thin-film disc is demonstrated. The quadrupole field is composed of the magnetic field that is generated by vortices on the disc introduced by cooling the disc across the transition temperature with a finite field and an oppositely directed uniform field applied after cooling. The trap is stable when all trapping processes are performed above the dendritic instability temperature T{sub a}. When the field intensity is changed below this temperature, the quadrupole field collapses and the trap disappears. The initial vortex density decreases even when the external field is changed at a temperature T>T{sub a}. However, the vortex density is stabilized at an equilibrium density, whereas at Tstable trap can be formed, even when the initial vortices are introduced through a dendritic avalanche.

  15. Modeling stable water isotopes using the UK Hadley Centre GCM

    NASA Astrophysics Data System (ADS)

    Tindall, J.; Valdes, P.; Sime, L.; Wolff, E.

    2005-12-01

    The representation of stable water isotopes in general circulation models (GCM's) is useful for interpreting paleodata and verifying simulations of past climate. Currently a number of GCM's are able to model water isotopes but most GCM's still do not have this facility. The Hadley Centre GCM (HadCM3) is a sophisticated, state-of-the-art, climate model which has been used for many present-day, paleoclimate and future studies, but previously has not included any representation of stable water isotopes. This feature has now been added as part of the ISOMAP (ISOtope calibration and MAPping) study. Here the implementation and simulations of stable water isotopes in HadCM3 will be discussed. Results for present day will be compared with observational datasets and other isotope enabled GCM's. The temporal variability of the modelled isotopes will also be examined and compared to storm track diagnostics.

  16. The Stable Symplectic category and a conjecture of Kontsevich

    E-print Network

    Nitu Kitchloo; Jack Morava

    2015-10-31

    We consider an oriented version of the stable symplectic category defined in \\cite{N}. We show that the group of monoidal automorphisms of this category, that fix each object, contains a natural subgroup isomorphic to the solvable quotient (or a graded-abelian quotient) of the Grothendieck--Teichm\\"uller group. This establishes a stable version of a conjecture of Kontsevich which states that groups closely related to the Grothendieck--Teichm\\"uller group act on the moduli space of certain field theories \\cite{KO}. The above quotient of the Grothendieck--Teichm\\"uller group is also shown to be the motivic group of monoidal automorphisms of a canonical representation (or fiber functor) on the stable symplectic category.

  17. Results of the Stable Microgravity Vibration Isolation Flight Experiment

    NASA Technical Reports Server (NTRS)

    Edberg, Donald; Boucher, Robert; Schenck, David; Nurre, Gerald; Whorton, Mark; Kim, Young; Alhorn, Dean

    1996-01-01

    This paper presents an overview of the STABLE microgravity isolation system developed and successfully flight tested in October 1995. A description of the hardware design and operational principles is given. A sample of the measured flight data is presented, including an evaluation of attenuation performance provided by the actively controlled electromagnetic isolation system. Preliminary analyses of flight data show that the acceleration environment aboard STABLE's isolated platform was attenuated by a factor of more than 25 between 0.1 and 100 Hz. STABLE was developed under a cooperative agreement between National Aeronautics and Space Administration, Marshall Space Flight Center, and McDonnell Douglas Aerospace. The flight hardware was designed, fabricated, integrated, tested, and delivered to the Cape during a five month period.

  18. Thermally stable crystalline mesoporous metal oxides with substantially uniform pores

    DOEpatents

    Wiesner, Ulrich; Orilall, Mahendra Christopher; Lee, Jinwoo; DiSalvo, Jr., Francis J

    2015-01-27

    Highly crystalline metal oxide-carbon composites, as precursors to thermally stable mesoporous metal oxides, are coated with a layer of amorphous carbon. Using a `one-pot` method, highly crystalline metal oxide-carbon composites are converted to thermally stable mesoporous metal oxides, having highly crystalline mesopore walls, without causing the concomitant collapse of the mesostructure. The `one-pot` method uses block copolymers with an sp or sp 2 hybridized carbon containing hydrophobic block as structure directing agents which converts to a sturdy, amorphous carbon material under appropriate heating conditions, providing an in-situ rigid support which maintains the pores of the oxides intact while crystallizing at temperatures as high as 1000 deg C. A highly crystalline metal oxide-carbon composite can be heated to produce a thermally stable mesoporous metal oxide consisting of a single polymorph.

  19. Stable multilayer thin films composed of gold nanoparticles and lysozyme

    NASA Astrophysics Data System (ADS)

    Su, Yan-lei; Li, Chao

    2008-01-01

    It needs appropriately attractive forces to construct multilayer thin films by layer-by-layer (LBL) assembly technique. It is feasible to prepare multilayer thin films on glass slides with negatively charged gold nanoparticles and positively charged lysozyme through the electrostatic LBL assembly technique. The gold nanoparticles/lysozyme multilayer thin films are highly stable; immersion in 0.1 M HCl, NaOH, and surfactant sodium dodecyl sulfate aqueous solutions cannot destroy the films. The highly stable gold nanoparticles/lysozyme multilayer thin films have potential application in long-term antibacterial coating.

  20. Fiber Optic Cable Thermal Preparation to Ensure Stable Operation

    NASA Technical Reports Server (NTRS)

    Thoames Jr, William J.; Chuska, Rick F.; LaRocca, Frank V.; Switzer, Robert C.; Macmurphy, Shawn L.; Ott, Melanie N.

    2008-01-01

    Fiber optic cables are widely used in modern systems that must provide stable operation during exposure to changing environmental conditions. For example, a fiber optic cable on a satellite may have to reliably function over a temperature range of -50 C up to 125 C. While the system requirements for a particular application will dictate the exact method by which the fibers should be prepared, this work will examine multiple ruggedized fibers prepared in different fashions and subjected to thermal qualification testing. The data show that if properly conditioned the fiber cables can provide stable operation, but if done incorrectly, they will have large fluctuations in transmission.

  1. Remarks on search methods for stable, massive, elementary particles

    NASA Astrophysics Data System (ADS)

    Perl, Martin L.

    2001-11-01

    This paper was presented at the 69th birthday celebration of Professor Eugene Commins, honoring his research achievements. These remarks are about the experimental techniques used in the search for new stable, massive particles, particles at least as massive as the electron. A variety of experimental methods such as accelerator experiments, cosmic ray studies, searches for halo particles in the galaxy and searches for exotic particles in bulk matter are described. A summary is presented of the measured limits on the existence of new stable, massive particle. .

  2. Synthesis and investigation of stable copper nanoparticle colloids

    NASA Astrophysics Data System (ADS)

    Tyurnina, A. E.; Shur, V. Ya.; Kozin, R. V.; Kuznetsov, D. K.; Pryakhina, V. I.; Burban, G. V.

    2014-07-01

    The synthesis of stable nanoparticle colloids by laser ablation of the copper target in water and fragmentation of Cu + CuO nanopowder with pulsed fiber laser irradiation with a wavelength of 1064 nm and pulse duration of 100 ns has been investigated experimentally. The influence of the technological parameters on the nanoparticle size and stability of the colloid has been studied. It has been shown that the laser ablation creates the CuO spherical nanoparticles. Subsequent fragmentation makes it possible to reduce the nanoparticle size in a colloid and to produce a stable colloidal solution from an aqueous suspension of Cu + CuO nanopowder.

  3. Prediction of stable walking for a toy that cannot stand.

    PubMed

    Coleman, M J; Garcia, M; Mombaur, K; Ruina, A

    2001-08-01

    Previous experiments [M. J. Coleman and A. Ruina, Phys. Rev. Lett. 80, 3658 (1998)] showed that a gravity-powered toy with no control and that has no statically stable near-standing configurations can walk stably. We show here that a simple rigid-body statically unstable mathematical model based loosely on the physical toy can predict stable limit-cycle walking motions. These calculations add to the repertoire of rigid-body mechanism behaviors as well as further implicating passive dynamics as a possible contributor to stability of animal motions. PMID:11497636

  4. Linear Fractional Stable Sheets: wavelet expansion and sample path properties

    E-print Network

    Ayache, Antoine; Xiao, Yimin

    2008-01-01

    In this paper we give a detailed description of the random wavelet series representation of real-valued linear fractional stable sheet introduced in Ayache, Roueff and Xiao (2007). By using this representation, in the case where the sample paths are continuous, an anisotropic uniform and quasi-optimal modulus of continuity of these paths is obtained as well as an upper bound for their behavior at infinity and around the coordinate axes. The Hausdorff dimensions of the range and graph of these stable random fields are then derived.

  5. Thermally stable surfactants and compositions and methods of use thereof

    DOEpatents

    Chaiko, David J. (Woodridge, IL)

    2008-09-02

    There are provided novel thermally stable surfactants for use with fillers in the preparation of polymer composites and nanocomposites. Typically, surfactants of the invention are urethanes, ureas or esters of thiocarbamic acid having a hydrocarbyl group of from 10 to 50 carbons and optionally including an ionizable or charged group (e.g., carboxyl group or quaternary amine). Thus, there are provided surfactants having Formula I: ##STR00001## wherein the variables are as defined herein. Further provided are methods of making thermally stable surfactants and compositions, including composites and nanocomposites, using fillers coated with the surfactants.

  6. Stable and unstable growth in molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Johnson, M. D.; Orme, C.; Hunt, A. W.; Graff, D.; Sudijono, J.; Sander, L. M.; Orr, B. G.

    1994-01-01

    We consider the growth of films by molecular beam epitaxy in the presence of step-edge (Schwoebel) barriers using numerical simulation and experiments. We show that the growth of a singular surface is unstable, but that a miscut above a certain critical slope (which depends on growth conditions) leads to stable growth in a step-flow mode. For singular surfaces the instability gives rise to the formation of large mounded structures on the surface for which the slope is in the stable regime. We identify these in GaAs epitaxy using atomic force and scanning tunneling microscopy. We propose a continuum equation which exhibits these features.

  7. Stable Isotopic Tracing—A Way Forward for Nanotechnology

    PubMed Central

    Gulson, Brian; Wong, Herbert

    2006-01-01

    Numerous publications and reports have expressed health and safety concerns about the production and use of nanoparticles, especially in areas of exposure monitoring, personal use, and environmental fate and transport. We suggest that stable isotopic tracers, which have been used widely in the earth sciences and in metabolic and other health-related studies for several decades, could be used to address many of these issues. One such example we are pursuing is the use of stable isotopes to monitor dermal absorption of zinc and titanium oxides in sunscreen preparations and other personal care products. Other potential applications of this tracing approach are discussed. PMID:17035130

  8. Next Generation JPL Ultra-Stable Trapped Ion Atomic Clocks

    NASA Technical Reports Server (NTRS)

    Burt, Eric; Tucker, Blake; Larsen, Kameron; Hamell, Robert; Tjoelker, Robert

    2013-01-01

    Over the past decade, trapped ion atomic clock development at the Jet Propulsion Laboratory (JPL) has focused on two directions: 1) new atomic clock technology for space flight applications that require strict adherence to size, weight, and power requirements, and 2) ultra-stable atomic clocks, usually for terrestrial applications emphasizing ultimate performance. In this paper we present a new ultra-stable trapped ion clock designed, built, and tested in the second category. The first new standard, L10, will be delivered to the Naval Research Laboratory for use in characterizing DoD space clocks.

  9. Maximum mass of stable magnetized highly super-Chandrasekhar white dwarfs: stable solutions with varying magnetic fields

    SciTech Connect

    Das, Upasana; Mukhopadhyay, Banibrata E-mail: bm@physics.iisc.ernet.in

    2014-06-01

    We address the issue of stability of recently proposed significantly super-Chandrasekhar white dwarfs. We present stable solutions of magnetostatic equilibrium models for super-Chandrasekhar white dwarfs pertaining to various magnetic field profiles. This has been obtained by self-consistently including the effects of the magnetic pressure gradient and total magnetic density in a general relativistic framework. We estimate that the maximum stable mass of magnetized white dwarfs could be more than 3 solar mass. This is very useful to explain peculiar, overluminous type Ia supernovae which do not conform to the traditional Chandrasekhar mass-limit.

  10. Molecular modeling of ultra-stable vapor deposited glasses

    NASA Astrophysics Data System (ADS)

    Singh, Sadanand; Averett, Devin; Chiu, Chi-Cheng; de Pablo, Juan J.

    2012-02-01

    Recent studies have shown that physical vapor deposition can be used to prepare glasses of small organic molecules with remarkably high kinetic stability and low enthalpy, particularly when compared to ordinary glasses prepared by cooling the supercooled liquid. The thermophysical properties of these new ultra-stable glasses are equivalent to those of common glasses after thousands of years of aging. However, experimental studies have so far been limited to relatively few types of molecules. We propose a molecular modeling scheme to prepare stable glasses that mimics the experimental procedure of vapor deposition. For simple disaccharides, such as trehalose, the thermophysical properties of our simulated glasses are consistent with those measured experimentally. We also prepare stable glasses of trehalose and glycerol mixtures, which are of interest for their use in stabilization of biomolecules in the glass state. Results for model binary Lennard-Jones glasses, which have been studied extensively in the literature, are also discussed. We find that the most stable glasses formed by vapor deposition are equivalent to ordinary glasses formed by cooling at a rate approximately 10 orders of magnitude slower than those accessible by ordinary cooling methods.

  11. LIMBUSTRACK: STABLE EYE-TRACKING IN IMPERFECT LIGHT Presented to

    E-print Network

    Duchowski, Andrew T.

    LIMBUSTRACK: STABLE EYE-TRACKING IN IMPERFECT LIGHT CONDITIONS A Thesis Presented to the Graduate. Dean Dr. Wayne Madison #12;Abstract Eye tracking research appears to have reached critical mass on Infra-Red (IR) illumination of the eyeball for eye tracking precision purposes it is often difficult

  12. COMBINING SOURCES IN STABLE ISOTOPE MIXING MODELS: ALTERNATIVE METHODS

    EPA Science Inventory

    Stable isotope mixing models are often used to quantify source contributions to a mixture. Examples include pollution source identification; trophic web studies; analysis of water sources for soils, plants, or water bodies; and many others. A common problem is having too many s...

  13. Stable isotopes, ecological integration and environmental change: wolves record atmospheric

    E-print Network

    climate change issues (Karl & Trenberth 2003; Kennedy 2004) and research on global carbon cyclingStable isotopes, ecological integration and environmental change: wolves record atmospheric carbon banksiana), large herbivore (moose, Alces alces) and large carnivore (grey wolf, Canis lupus) from North

  14. DISPERSAL OF STABLE FLIES FROM LARVAL DEVELOPMENTAL SITES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A large scale stable fly mark recapture study was conducted at the Agricultural Research and Development Center, Ithaca, Nebraska. Three developmental sites were marked with fluorescent powder. Flies picked up the powder as they emerged from these sites and were marked. A grid of 87 Broce sticky tra...

  15. Possible Potentials Responsible for Stable Circular Relativistic Orbits

    ERIC Educational Resources Information Center

    Kumar, Prashant; Bhattacharya, Kaushik

    2011-01-01

    Bertrand's theorem in classical mechanics of the central force fields attracts us because of its predictive power. It categorically proves that there can only be two types of forces which can produce stable, circular orbits. In this paper an attempt has been made to generalize Bertrand's theorem to the central force problem of relativistic…

  16. Highly Stable Silver Nanoplates for Surface Plasmon Resonance Biosensing

    SciTech Connect

    Gao, Chuanbo; Lu, Zhenda; Chi, Miaofang; Liu, ying; Cheng, Quan; Yin, Yadong

    2012-01-01

    An SPR biosensor was developed by employing highly stable Au-protected Ag nanoplates (NP) as enhancers (see picture). Superior performance was achieved by depositing a thin and uniform coating of Au on the Ag surface while minimizing disruptive galvanic replacement and retaining the strong surface plasmon resonance (SPR) of the silver nanoplates.

  17. Pollen as a tool for tracking stable flies.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The stable fly, (Stomoxys calcitrans L.), is an important pest of humans and livestock in many parts of the world. Its immature stages develop in decaying vegetation, e.g. hya, silage, feed, mulch and grass clippings, in agricultural and urban areas. although both sexes are oligate blood feeders, ...

  18. bounding the number of stable homotopy types of a parametrized ...

    E-print Network

    However, two closed and bounded semi-algebraic sets which are stable ... defined by quadratic inequalities, and he defined a certain spectral sequence con- ... realizable sign conditions on P. For ? ? Sign(P) we define the level of ? as the ... positive and smaller than any positive element of R. When a ? R??? is bounded.

  19. Functional Stable Model Semantics and Answer Set Programming Modulo Theories

    E-print Network

    of work focuses on improving the compu- tational efficiency by integrating ASP with other declarative answer set programming. We demonstrate that the functional stable model se- mantics plays an important programs can be translated into SMT instances, which is sim- ilar to the known relationship between ASP

  20. Stable isotopes sales: Mound customer and shipment summaries, FY 1985

    SciTech Connect

    Flayler, K.A.

    1987-12-15

    A listing is given of Mound's sales of stable isotopes of noble gases, deuterium, carbon, oxygen, nitrogen, chlorine, bromine, and sulfur for fiscal year 1985. Purchasers are listed alphabetically and are divided into domestic and foreign groups. A cross-reference index by location is included for domestic and foreign customers. Cross-reference listings by isotope purchased are included for all customers.

  1. Stable isotope sales: Mound customer and shipment summaries, FY 1986

    SciTech Connect

    Kramer, L.R.; Flayler, K.A.

    1988-05-20

    A listing is given of Mound's sales of stable isotopes of noble gases, carbon, oxygen, nitrogen, chlorine, and sulfur for fiscal year 1986. Purchasers are listed alphabetically and are divided into domestic and foreign groups. Cross-reference indexes by location and by isotope are included for all customers. 3 tabs.

  2. USE OF STABLE ISOTOPES IN ENVIRONMENTAL AND FORENSIC GEOCHEMISTRY STUDIES

    EPA Science Inventory

    Stable carbon and hydrogen isotopes have been used for many decades in the petroleum industry, but the development of combined gas chromatography-isotope ratio mass spectrometry (GCIRMS) has led to a virtual explosion in application of this technique not only in petroleum explora...

  3. SOURCE PARTITIONING USING STABLE ISOTOPES: COPING WITH TOO MANY SOURCES

    EPA Science Inventory

    Stable isotopes are increasingly being used as tracers in environmental studies. One application is to use isotopic ratios to quantitatively determine the proportional contribution of several sources to a mixture, such as the proportion of various pollution sources in a waste st...

  4. Three-dimensional stable matching with cyclic preferences

    E-print Network

    Enquist, Magnus

    ­209] showed that not all instances of 3GSM allow stable matchings. Boros et al. [Boros, E., Gurvich, V, and dogs care only about women. The origin of this problem is attributed to Knuth. Recently, Boros et al the partial result of Boros et al. by proving stability of cyclic 3GSM for n=4. The proof, given in Section 3

  5. STABLE ISOTOPES AS INDICATORS OF SOIL WATER DYNAMICS IN WATERSHEDS

    EPA Science Inventory

    Stream water quality and quantity depend on discharge rates of water and nutrients from soils. However, soil-water storage is very dynamic and strongly influenced by plants. We analyzed stable isotopes of oxygen and hydrogen to quantify spatial and temporal changes in evaporati...

  6. Dielectric Relaxation of Materials that Form Ultra-Stable Glasses

    NASA Astrophysics Data System (ADS)

    Richert, Ranko

    2015-03-01

    Physical vapor deposition of glass forming materials onto substrates at temperatures around 0.8 Tg produces glasses of high density and low enthalpy. Using interdigitated electrode cells as substrates, such stable glasses can be studied by dielectric spectroscopy in situ. This technique is applied to monitor the dynamics of stable films upon their conversion to the ordinary supercooled liquid state. The dielectric loss during transformation indicates that the softening proceeds by a growth front mechanism and generates the ordinary liquid state without forming intermediates. The same technique is also used to assess the residual dynamics of the stable glassy state. We observe that processes such as the Johari-Goldstein beta relaxation are strongly suppressed in this stable state, consistent with the relatively low fictive temperature of these glassy states. coauthors: Hai-Bin Yu, Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85278; Michael Tylinski, and Mark D. Ediger, Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706.

  7. Superradiantly stable non-extremal Reissner-Nordstrom black holes

    E-print Network

    Jia-Hui Huang; Zhan-Feng Mai

    2015-03-04

    The superradiant stability is investigated for non-extremal Reissner-Nordstrom black hole. We use an algebraic method to demonstrate that all non-extremal Reissner-Nordstrom black holes are superradiantly stable against a charged massive scalar perturbation. This improves the results obtained before for non-extremal Reissner-Nordstrom black holes.

  8. Design of Hard Water Stable Emulsifier Systems for Petroleum-

    E-print Network

    Clarens, Andres

    Design of Hard Water Stable Emulsifier Systems for Petroleum- and Bio-based Semi for petroleum and bio-based MWFs that improve fluid lifetime by providing emulsion stability under hard water. The newly developed petroleum and bio-based formulations with improved hard water stability are competitive

  9. ESTIMATING THE TIMING OF DIET SHIFTS USING STABLE ISOTOPES

    EPA Science Inventory

    Stable isotope analysis has become an important tool in studies of trophic food webs and animal feeding patterns. When animals undergo rapid dietary shifts due to migration, metamorphosis, or other reasons, the isotopic composition of their tissues begins changing to reflect tha...

  10. DECOUPLED ENERGY STABLE SCHEMES FOR A PHASE-FIELD ...

    E-print Network

    2014-04-24

    schemes for the coupled nonlinear phase-field model are constructed and ..... Taking the variation of A(x) with respect to these volume preserving flow map for ...... An energy law preserving C0 finite element scheme for simulating the kinematic ... A systematic methodology for constructing high-order energy stable weno.

  11. RESEARCH ARTICLE Directional flow sensing by passively stable larvae

    E-print Network

    Fuchs, Heidi L.

    RESEARCH ARTICLE Directional flow sensing by passively stable larvae Heidi L. Fuchs1, *, Adam J a horizontal axis elicited the diving response observed previously for oyster larvae in turbulence. The results provide strong evidence that the turbulence-sensing mechanism relies on gravity-detecting organs

  12. Stable vortex loops in two-species BECs

    NASA Astrophysics Data System (ADS)

    Bedaque, P. F.; Berkowitz, E.; Sen, Srimoyee

    2012-11-01

    We consider the creation of stable, stationary closed vortex loops, analogues of vortons in dense matter and superconducting cosmic strings in cold atom BECs. We explore the parameter region where these solutions are likely to exist and comment on methods to create them experimentally.

  13. Stable vortex loops in two-species BECs

    E-print Network

    Bedaque, Paulo F; Sen, Srimoyee

    2011-01-01

    We consider the creation of stable, stationary closed vortex loops, analogue to the vortons and superconducting cosmic strings, in cold atom BEC's. We explore the parameter region where these solutions are likely to exist and comment on methods to create them experimentally.

  14. Stable vortex loops in two-species BECs

    E-print Network

    Paulo F. Bedaque; Evan Berkowitz; Srimoyee Sen

    2011-11-18

    We consider the creation of stable, stationary closed vortex loops, analogue to the vortons and superconducting cosmic strings, in cold atom BEC's. We explore the parameter region where these solutions are likely to exist and comment on methods to create them experimentally.

  15. Stable periodic billiard paths in obtuse isosceles triangles

    E-print Network

    Hooper, Patrick

    Stable periodic billiard paths in obtuse isosceles triangles W. Patrick Hooper March 27, 2006 Can you place a small billiard ball on a frictionless triangular pool table and hit it so that it comes dynamics s # of a periodic billiard path # is the bi­infinite sequence of edges the billiard path hits

  16. Stable periodic billiard paths in obtuse isosceles triangles

    E-print Network

    Hooper, Patrick

    Stable periodic billiard paths in obtuse isosceles triangles W. Patrick Hooper March 27, 2006 Can you place a small billiard ball on a frictionless triangular pool table and hit it so that it comes dynamics s of a periodic billiard path is the bi-infinite sequence of edges the billiard path hits, which

  17. Apparatus and method for monitoring of gas having stable isotopes

    DOEpatents

    Clegg, Samuel M; Fessenden-Rahn, Julianna E

    2013-03-05

    Gas having stable isotopes is monitored continuously by using a system that sends a modulated laser beam to the gas and collects and transmits the light not absorbed by the gas to a detector. Gas from geological storage, or from the atmosphere can be monitored continuously without collecting samples and transporting them to a lab.

  18. INCORPORATING CONCENTRATION DEPENDENCE IN STABLE ISOTOPE MIXING MODELS

    EPA Science Inventory

    Stable isotopes are frequently used to quantify the contributions of multiple sources to a mixture; e.g., C and N isotopic signatures can be used to determine the fraction of three food sources in a consumer's diet. The standard dual isotope, three source linear mixing model ass...

  19. INCORPORATING CONCENTRATION DEPENDENCE IN STABLE ISOTOPE MIXING MODELS

    EPA Science Inventory

    Stable isotopes are often used as natural labels to quantify the contributions of multiple sources to a mixture. For example, C and N isotopic signatures can be used to determine the fraction of three food sources in a consumer's diet. The standard dual isotope, three source li...

  20. Development of stable isotope mixing models in ecology - Sydney

    EPA Science Inventory

    More than 40 years ago, stable isotope analysis methods used in geochemistry began to be applied to ecological studies. One common application is using mathematical mixing models to sort out the proportional contributions of various sources to a mixture. Examples include contri...