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Sample records for carlo c-h bond

  1. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

    Science.gov (United States)

    Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

    2014-09-14

    An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

  2. Directed C-H Bond Oxidation of (+)-Pleuromutilin.

    Science.gov (United States)

    Ma, Xiaoshen; Kucera, Roman; Goethe, Olivia F; Murphy, Stephen K; Herzon, Seth B

    2018-05-01

    Antibiotics derived from the diterpene fungal metabolite (+)-pleuromutilin (1) are useful agents for the treatment Gram-positive infections in humans and farm animals. Pleuromutilins elicit slow rates of resistance development and minimal cross-resistance with existing antibiotics. Despite efforts aimed at producing new derivatives by semisynthesis, modification of the tricyclic core is underexplored, in part due to a limited number of functional group handles. Herein, we report methods to selectively functionalize the methyl groups of (+)-pleuromutilin (1) by hydroxyl-directed iridium-catalyzed C-H silylation, followed by Tamao-Fleming oxidation. These reactions provided access to C16, C17, and C18 monooxidized products, as well as C15/C16 and C17/C18 dioxidized products. Four new functionalized derivatives were prepared from the protected C17 oxidation product. C6 carboxylic acid, aldehyde, and normethyl derivatives were prepared from the C16 oxidation product. Many of these sequences were executed on gram scales. The efficiency and practicality of these routes provides an easy method to rapidly interrogate structure-activity relationships that were previously beyond reach. This study will inform the design of fully synthetic approaches to novel pleuromutilins and underscores the power of the hydroxyl-directed iridium-catalyzed C-H silylation reaction.

  3. Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds.

    Science.gov (United States)

    Choi, Jongwook; Choliy, Yuriy; Zhang, Xiawei; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

    2009-11-04

    (PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH(3))(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and alpha-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

  4. Oxidative addition of C--H bonds in organic molecules to transition metal centers

    International Nuclear Information System (INIS)

    Bergman, R.G.

    1989-04-01

    Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs

  5. Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

    Science.gov (United States)

    Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

    2015-01-28

    (1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

  6. C-H Bond Functionalization via Hydride Transfer: Direct Coupling of Unactivated Alkynes and sp3 C-H Bonds Catalyzed by Platinum Tetraiodide

    Science.gov (United States)

    Vadola, Paul A.; Sames, Dalibor

    2010-01-01

    We report a catalytic intramolecular coupling between terminal unactivated alkynes and sp3 C-H bonds via the through-space hydride transfer (HT-cyclization of alkynes). This method enables one-step preparation of complex heterocyclic compounds by α-alkenylation of readily available cyclic ethers and amines. We show that PtI4 is an effective Lewis acid catalyst for the activation of terminal alkynes for the hydride attack and subsequent C-C bond formation. In addition, we have shown that the activity of neutral platinum salts (PtXn) can be modulated by the halide ligands. This modulation in turn allows for fine-tuning of the platinum center reactivity to match the reactivity and stability of selected substrates and products. PMID:19852462

  7. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  8. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

    Science.gov (United States)

    Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

    2016-11-10

    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  9. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  10. Cobalt-Catalyzed, Aminoquinoline-Directed sp2 C-H Bond Alkenylation by Alkynes**

    Science.gov (United States)

    Grigorjeva, Liene; Daugulis, Olafs

    2014-01-01

    We have developed a method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed sp2 C-H bond alkenylation by alkynes. Method shows excellent functional group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2*4H2O catalyst, Mn(OAc)2 cocatalyst, and oxygen from air as a terminal oxidant. PMID:25060365

  11. Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

    Directory of Open Access Journals (Sweden)

    Yong Liang

    2015-03-01

    Full Text Available Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

  12. Infrared matrix isolation study of hydrogen bonds involving C-H bonds: Substituent effects

    International Nuclear Information System (INIS)

    Jeng, M.L.H.; Ault, B.S.

    1989-01-01

    The matrix isolation technique combined with infrared spectroscopy has been employed to isolate and characterize hydrogen-bonded complexes between a series of substituted alkynes and several oxygen and nitrogen bases. Distinct evidence for hydrogen bond formation was observed in each case, with a characteristic red shift of the hydrogen stretching motion ν r . Shifts between 100 and 300 cm -1 were observed, the largest being for the complex of CF 3 CCH with (CH 3 ) 3 N. The perturbed carbon-carbon triple bond stretching vibration was observed for most complexes, as was the alkynic hydrogen bending motion. Attempts were made to correlate the magnitude of the red shift of ν s with substituent constants for the different substituted alkynes; a roughly linear correlation was found with the Hammett σ parameter. Lack of correlation Δν s with either σ 1 or σ R alone suggests that both inductive and resonance contributions to the strength of the hydrogen-bonding interaction are important

  13. Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

    Energy Technology Data Exchange (ETDEWEB)

    Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.

    2004-11-27

    Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

  14. Direct α-C-H bond functionalization of unprotected cyclic amines

    Science.gov (United States)

    Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

    2018-02-01

    Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

  15. Borylnitrenes: electrophilic reactive intermediates with high reactivity towards C-H bonds.

    Science.gov (United States)

    Bettinger, Holger F; Filthaus, Matthias

    2010-12-21

    Borylnitrenes (catBN 3a and pinBN 3b; cat = catecholato, pin = pinacolato) are reactive intermediates that show high tendency towards insertion into the C-H bonds of unactivated hydrocarbons. The present article summarizes the matrix isolation investigations that were aimed at identifying, characterizing and investigating the chemical behaviour of 3a by spectroscopic means, and of the experiments in solution and in the gas phase that were performed with 3b. Comparison with the reactivity reported for difluorovinylidene 1a in solid argon indicates that 3a shows by and large similar reactivity, but only after photochemical excitation. The derivative 3b inserts into the C-H bonds of hydrocarbon solvents in high yields and thus allows the formation of primary amines, secondary amines, or amides from "unreactive" hydrocarbons. It can also be used for generation of methylamine or methylamide from methane in the gas phase at room temperature. Remaining challenges in the chemistry of borylnitrenes are briefly summarized.

  16. Activation of C-H bond in methane by Pd atom from the bonding evolution theory perspective.

    Science.gov (United States)

    Nizovtsev, Anton S

    2013-08-15

    We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques. Copyright © 2013 Wiley Periodicals, Inc.

  17. Hydrogenation of graphene nanoflakes and C-H bond dissociation of hydrogenated graphene nanoflakes: a density functional theory study

    Institute of Scientific and Technical Information of China (English)

    Sheng Tao; Hui-Ting Liu; Liu-Ming Yan; Bao-Hua Yue; Ai-Jun Li

    2017-01-01

    The Gibbs free energy change for the hydrogenation of graphene nanoflakes Cn (n =24,28,30 and 32) and the C-H bond dissociation energy of hydrogenated graphene nanoflakes CnHm (n =24,28,30 and 32;and m =1,2 and 3) are evaluated using density functional theory calculations.It is concluded that the graphene nanoflakes and hydrogenated graphene nanoflakes accept the ortharyne structure with peripheral carbon atoms bonded via the most triple bonds and leaving the least unpaired dangling electrons.Five-membered rings are formed at the deep bay sites attributing to the stabilization effect from the pairing of dangling electrons.The hydrogenation reactions which eliminate one unpaired dangling electron and thus decrease the overall multiplicity of the graphene nanoflakes or hydrogenated graphene nanoflakes are spontaneous with negative or near zero Gibbs free energy change.And the resulting C-H bonds are stable with bond dissociation energy in the same range as those of aromatic compounds.The other C-H bonds are not as stable attributing to the excessive unpaired dangling electrons being filled into the C-H anti-bond orbital.

  18. Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

    Science.gov (United States)

    Corbin, Joshua R; Schomaker, Jennifer M

    2017-04-13

    Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

  19. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan

    2008-02-04

    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  20. Origin of the Ability of α-Fe2 O3 Mesopores to Activate C-H Bonds in Methane.

    Science.gov (United States)

    Dong, Bing; Han, Zhen; Zhang, Yongbo; Yu, Youyi; Kong, Aiguo; Shan, Yongkui

    2016-02-01

    Methane is a most abundant and inexpensive hydrocarbon feedstock for the production of chemicals and fuels. However, it is extremely difficult to directly convert methane to higher hydrocarbons because the C-H bonds in methane are the most stable C-H bonds of all hydrocarbons. The activation of the C-H bonds in methane by using an efficient and mild route remains a daunting challenge. Here, we show that the inner surface structures of the pore walls in mesoporous α-Fe 2 O 3 possess excellent catalytic performance for methane activation and convert C-H bonds into the C-O bonds in an O 2 atmosphere at 140 °C. We found that such unusual structures are mainly comprised of turbostratic ribbons and K crystal faces and have higher catalytic activity than the (110) plane. These results are without precedent in the history of catalysis chemistry and will provide a new pathway for designing and preparing highly efficient catalytic materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Eosin Y as a Direct Hydrogen Atom Transfer Photocatalyst for the Functionalization of C-H Bonds.

    Science.gov (United States)

    Fan, Xuan-Zi; Rong, Jia-Wei; Wu, Hao-Lin; Zhou, Quan; Deng, Hong-Ping; Tan, Jin Da; Xue, Cheng-Wen; Wu, Li-Zhu; Tao, Hai-Rong; Wu, Jie

    2018-05-02

    Eosin Y, a well-known economical alternative to metal catalysts in visible-light-driven single-electron transfer-based organic transformations, can behave as an effective direct hydrogen atom transfer catalyst for C-H activation. Using the alkylation of C-H bonds with electron-deficient alkenes as a model study revealed an extremely broad substrate scope, enabling easy access to a variety of important synthons. This eosin Y-based photocatalytic hydrogen atom transfer strategy is promising for diverse functionalization of a wide range of native C-H bonds in a green and sustainable manner. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Solution Phase Measurement of Both Weak Sigma and C-H---X- Hydrogen Bonding Interactions in Synthetic Anion Receptors

    Energy Technology Data Exchange (ETDEWEB)

    Berryman, Mr. Orion B. [University of Oregon; Sather, Mr. Aaron C [University of Oregon; Hay, Benjamin [ORNL; Meisner, Mr. Jeffrey S. [University of Oregon; Johnson, Prof. Darren W. [University of Oregon

    2008-01-01

    A series of tripodal receptors preorganize electron-deficient aromatic rings to bind halides in organic solvents using weak sigma anion-to-arene interactions or C-H---X- hydrogen bonds. 1H NMR spectroscopy proves to be a powerful technique for quantifying binding in solution, and determining the interaction motifs, even in cases of weak binding.

  3. UV-light promoted C-H bond activation of benzene and fluorobenzenes by an iridium(i) pincer complex.

    Science.gov (United States)

    Hauser, Simone A; Emerson-King, Jack; Habershon, Scott; Chaplin, Adrian B

    2017-03-28

    Iridium(i) carbonyl complex [Ir(2,6-(P t Bu 2 CH 2 ) 2 C 6 H 3 )(CO)] undergoes reversible C-H bond activation of benzene and a series of fluorobenzenes on UV irradiation. Exclusive ortho-selectivity is observed in reactions of fluorobenzene and 1,2-difluorobenzene.

  4. Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, Roberg G.; Gribble, Jr., Michael W.; Ellman, Jonathan A.

    2008-01-30

    The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.

  5. Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.

    Science.gov (United States)

    Wang, Teng; Jiao, Ning

    2014-04-15

    Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our

  6. Ligand-accelerated activation of strong C-H bonds of alkanes by a (salen)ruthenium(VI)-nitrido complex.

    Science.gov (United States)

    Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Yiu, Shek-Man; Lau, Tai-Chu

    2012-09-03

    Kinetic and mechanistic studies on the intermolecular activation of strong C-H bonds of alkanes by a (salen)ruthenium(VI) nitride were performed. The initial, rate-limiting step, the hydrogen atom transfer (HAT) from the alkane to Ru(VI)≡N, generates Ru(V)=NH and RC·HCH(2)R. The following steps involve N-rebound and desaturation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation.

    Science.gov (United States)

    Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng

    2015-08-21

    A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

  8. Late metal carbene complexes generated by multiple C-H activations: examining the continuum of M=C bond reactivity.

    Science.gov (United States)

    Whited, Matthew T; Grubbs, Robert H

    2009-10-20

    Unactivated C(sp(3))-H bonds are ubiquitous in organic chemicals and hydrocarbon feedstocks. However, these resources remain largely untapped, and the development of efficient homogeneous methods for hydrocarbon functionalization by C-H activation is an attractive and unresolved challenge for synthetic chemists. Transition-metal catalysis offers an attractive possible means for achieving selective, catalytic C-H functionalization given the thermodynamically favorable nature of many desirable partial oxidation schemes and the propensity of transition-metal complexes to cleave C-H bonds. Selective C-H activation, typically by a single cleavage event to produce M-C(sp(3)) products, is possible through myriad reported transition-metal species. In contrast, several recent reports have shown that late transition metals may react with certain substrates to perform multiple C-H activations, generating M=C(sp(2)) complexes for further elaboration. In light of the rich reactivity of metal-bound carbenes, such a route could open a new manifold of reactivity for catalytic C-H functionalization, and we have targeted this strategy in our studies. In this Account, we highlight several early examples of late transition-metal complexes that have been shown to generate metal-bound carbenes by multiple C-H activations and briefly examine factors leading to the selective generation of metal carbenes through this route. Using these reports as a backdrop, we focus on the double C-H activation of ethers and amines at iridium complexes supported by Ozerov's amidophosphine PNP ligand (PNP = [N(2-P(i)Pr(2)-4-Me-C(6)H(3))(2)](-)), allowing isolation of unusual square-planar iridium(I) carbenes. These species exhibit reactivity that is distinct from the archetypal Fischer and Schrock designations. We present experimental and theoretical studies showing that, like the classical square-planar iridium(I) organometallics, these complexes are best described as nucleophilic at iridium. We discuss

  9. Multiple C-H Bond Activations and Ring-Opening C-S Bond Cleavage of Thiophene by Dirhenium Carbonyl Complexes.

    Science.gov (United States)

    Adams, Richard D; Dhull, Poonam; Tedder, Jonathan D

    2018-06-14

    The reaction of Re 2 (CO) 8 (μ-C 6 H 5 )(μ-H) (1) with thiophene in CH 2 Cl 2 at 40 °C yielded the new compound Re 2 (CO) 8 (μ-η 2 -SC 4 H 3 )(μ-H) (2), which contains a bridging σ-π-coordinated thienyl ligand formed by the activation of the C-H bond at the 2 position of the thiophene. Compound 2 exhibits dynamical activity on the NMR time scale involving rearrangements of the bridging thienyl ligand. The reaction of compound 2 with a second 1 equiv of 1 at 45 °C yielded the doubly metalated product [Re 2 (CO) 8 (μ-H)] 2 (μ-η 2 -2,3-μ-η 2 -4,5-C 4 H 2 S) (3), formed by the activation of the C-H bond at the 5 position of the thienyl ligand in 2. Heating 3 in a hexane solvent to reflux transformed it into the ring-opened compound Re(CO) 4 [μ-η 5 -η 2 -SCC(H)C(H)C(H)][Re(CO) 3 ][Re 2 (CO) 8 (μ-H)] (4) by the loss of one CO ligand. Compound 4 contains a doubly metalated 1-thiapentadienyl ligand formed by the cleavage of one of the C-S bonds. When heated to reflux (125 °C) in an octane solvent in the presence of H 2 O, the new compound Re(CO) 4 [η 5 -μ-η 2 -SC(H)C(H)C(H)C(H)]Re(CO) 3 (5) was obtained by cleavage of the Re 2 (CO) 8 (μ-H) group from 4 with formation of the known coproduct [Re(CO) 3 (μ 3 -OH)] 4 . All new products were characterized by single-crystal X-ray diffraction analyses.

  10. Alkane Activation at Ambient Temperatures: Unusual Selectivities, C-C, C-H Bond Scission versus C-C Bond Coupling

    NARCIS (Netherlands)

    Trionfetti, C.; Agiral, A.; Gardeniers, Johannes G.E.; Lefferts, Leonardus; Seshan, Kulathuiyer

    2008-01-01

    Activating bonds: A cold plasma generated by dielectric barrier discharge in a microreactor converts alkanes (C1–C3) at atmospheric pressure. Large amounts of products with higher molecular weight than the starting hydrocarbons are observed showing that C-H activation at lower T favourably leads to

  11. Aromatic C-H bond activation revealed by infrared multiphoton dissociation spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Jašíková, L.; Hanikýřová, E.; Schröder, Detlef; Roithová, J.

    2012-01-01

    Roč. 47, č. 4 (2012), s. 460-465 ISSN 1076-5174 Grant - others:GA ČR(CZ) GAP207/11/0338; Seventh Framework Program(XE) 226716 Institutional research plan: CEZ:AV0Z40550506 Keywords : C-H activation * density functional theory calculations * ion spectroscopy * metal oxides * rearrangements Subject RIV: CC - Organic Chemistry Impact factor: 3.214, year: 2012

  12. Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C-H bond activation.

    Science.gov (United States)

    Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu; Liu, Xiao; Gong, Jinlong

    2017-06-01

    Heterogeneous metal complex catalysts for direct C-H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2'-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)] 2 (Cp* = η 5 -pentamethylcyclopentadienyl) and [Ir(cod)(OMe)] 2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C-H oxidation of heterocycles and cycloalkanes as well as C-H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13 C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations.

  13. Mild Palladium Catalyzed ortho C-H Bond Functionalizations of Aniline Derivatives.

    Science.gov (United States)

    Tischler, Ms Orsolya; Tóth, Mr Balázs; Novák, Zoltán

    2017-02-01

    This account collects the developments and transformations which avoid the utilization of harsh reaction conditions in the field of palladium catalyzed, ortho-directed C-H activation of aniline derivatives from the first attempts to up-to-date results, including the results of our research laboratory. The discussed functionalizations performed under mild conditions include acylation, olefination, arylation, alkylation, alkoxylation reactions. Beside the optimization studies and the synthetic applications mechanistic investigations are also presented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

    Science.gov (United States)

    Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.

    2018-02-01

    The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

  15. C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

    OpenAIRE

    Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

    2012-01-01

    We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexib...

  16. Salt-Free Strategy for the Insertion of CO2 into C-H Bonds: Catalytic Hydroxymethylation of Alkynes.

    Science.gov (United States)

    Wendling, Timo; Risto, Eugen; Krause, Thilo; Gooßen, Lukas J

    2018-04-20

    A copper(I) catalyst enables the insertion of carbon dioxide into alkyne C-H bonds by using a suitable organic base with which hydrogenation of the resulting carboxylate salt with regeneration of the base becomes thermodynamically feasible. In the presence of catalytic copper(I) chloride/4,7-diphenyl-1,10-phenanthroline, polymer-bound triphenylphosphine, and 2,2,6,6-tetramethylpiperidine as the base, terminal alkynes undergo carboxylation at 15 bar CO 2 and room temperature. After filtration, the ammonium alkynecarboxylate can be hydrogenated to the primary alcohol and water at a rhodium/molybdenum catalyst, regenerating the amine base. This demonstrates the feasibility of a salt-free overall process, in which carbon dioxide serves as a C1 building block in a C-H functionalization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Understanding trends in C-H bond activation in heterogeneous catalysis.

    Science.gov (United States)

    Latimer, Allegra A; Kulkarni, Ambarish R; Aljama, Hassan; Montoya, Joseph H; Yoo, Jong Suk; Tsai, Charlie; Abild-Pedersen, Frank; Studt, Felix; Nørskov, Jens K

    2017-02-01

    While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.

  18. Metal-organic cooperative catalysis in C-H and C-C bond activation and its concurrent recovery.

    Science.gov (United States)

    Park, Young Jun; Park, Jung-Woo; Jun, Chul-Ho

    2008-02-01

    The development of an efficient catalytic activation (cleavage) system for C-H and C-C bonds is an important challenge in organic synthesis, because these bonds comprise a variety of organic molecules such as natural products, petroleum oils, and polymers on the earth. Among many elegant approaches utilizing transition metals to activate C-H and C-C bonds facilely, chelation-assisted protocols based on the coordinating ability of an organic moiety have attracted great attention, though they have often suffered from the need for an intact coordinating group in a substrate. In this Account, we describe our entire efforts to activate C-H or C-C bonds adjacent to carbonyl groups by employing a new concept of metal-organic cooperative catalysis (MOCC), which enables the temporal installation of a 2-aminopyridyl group into common aldehydes or ketones in a catalytic way. Consequently, a series of new catalytic reactions such as alcohol hydroacylation, oxo-ester synthesis, C-C triple bond cleavage, hydrative dimerization of alkynes, and skeletal rearrangements of cyclic ketones was realized through MOCC. In particular, in the quest for an optimized MOCC system composed of a Wilkinson's catalyst (Ph 3P) 3RhCl and an organic catalyst (2-amino-3-picoline), surprising efficiency enhancements could be achieved when benzoic acid and aniline were introduced as promoters for the aldimine formation process. Furthermore, a notable accomplishment of C-C bond activation has been made using 2-amino-3-picoline as a temporary chelating auxiliary in the reactions of unstrained ketones with various terminal olefins and Wilkinson's catalyst. In the case of seven-membered cyclic ketones, an interesting ring contraction to five- or six-membered ones takes place through skeletal rearrangements initiated by the C-C bond activation of MOCC. On the other hand, the fundamental advances of these catalytic systems into recyclable processes could be achieved by immobilizing both metal and organic

  19. Rhodium catalyzed regioselective arene homologation of aryl urea via double C-H bond activation and migratory insertion of alkyne

    Institute of Scientific and Technical Information of China (English)

    Yan Wang; Hao Zhou; Ke Xu; Mei-Hua Shen; Hua-Dong Xu

    2017-01-01

    A convenient rhodium catalyzed oxidative arene homologation of aniline derivatives with symmetrical or unsymmetrical alkynes using Cu(OAc)2 as oxidant is described.Urea group is shown to be effective as a directing group for initial ortho C-H activation.Two migratory insertion events of alkyne into Rh-C bond occur successively,both with complete regioselectivity.This method is particularly useful for synthesis of polyarenes with different substituents,which has not been reported with conventional protocol.A mechanism has been proposed to explain the observed data.

  20. Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

    Science.gov (United States)

    Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

    2017-09-19

    As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

  1. Monte Carlo simulation of AB-copolymers with saturating bonds

    DEFF Research Database (Denmark)

    Chertovich, A.C.; Ivanov, V.A.; Khokhlov, A.R.

    2003-01-01

    Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A- and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending...

  2. Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor.

    Science.gov (United States)

    Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling

    2018-02-16

    A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

  3. Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds.

    Science.gov (United States)

    Bhowmick, Ranadeep; Rajasekaran, Srivats; Friebel, Daniel; Beasley, Cara; Jiao, Liying; Ogasawara, Hirohito; Dai, Hongjie; Clemens, Bruce; Nilsson, Anders

    2011-04-13

    Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. © 2011 American Chemical Society

  4. Quantification of the selective activation of C--H bonds in short chain alkanes: The reactivity of ethane, propane, isobutane, n-butane, and neopentane on Ir(111)

    International Nuclear Information System (INIS)

    Johnson, D.F.; Weinberg, W.H.

    1995-01-01

    The initial probabilities of precursor-mediated, dissociative chemisorption of the saturated hydrocarbons 13 C-labeled ethane, propane, isobutane, n-butane, and neopentane on the close-packed Ir(111) surface have been measured. The selective activation of primary (1 degree), secondary (2 degree), and tertiary (3 degree) C--H bonds has been quantified by examining the reactivities of the selectively deuterated isotopomers of propane, C 3 H 8 , CH 3 CD 2 CH 3 , and C 3 D 8 , and of isobutane, (CH 3 ) 3 CH, (CH 3 ) 3 CD, and (CD 3 ) 3 CH. With respect to the bottom of the physically adsorbed well for each hydrocarbon, the apparent C--H bond activation energies have been found to be 10.4±0.3 kcal/mol (ethane), 11.4±0.3 kcal/mol (propane), 11.5±0.3 kcal/mol (n-butane), 11.3±0.3 kcal/mol (i-butane), and 11.3±0.3 kcal/mol (neopentane). For all the alkanes examined, the ratios of the preexponential factors of the rate coefficients of reaction and desorption are 1x10 -2 . The C--D bond activation energies are higher than the corresponding C--H bond activation energies by 480 cal/mol (ethane), 630 cal/mol (propane), and 660 cal/mol (i-butane). By analyzing the primary kinetic isotope effects for the selectively deuterated isotopomers of propane and isobutane, the 2 degree C--H bond activation energy is found to be 310±160 cal/mol less than the 1 degree C--H bond activation energy on this surface, and similarly, 3 degree C--H bond cleavage is less by 80±70 cal/mol. The quantification of the branching ratios within the C--H bond activation channel for propane and isobutane on this surface shows that the formation of 1 degree-alkyl intermediates is, in general, favored over the formation of either 2 degree- or 3 degree-alkyl intermediates. (Abstract Truncated)

  5. Palladium-catalyzed meta-selective C-H bond activation with a nitrile-containing template: computational study on mechanism and origins of selectivity.

    Science.gov (United States)

    Yang, Yun-Fang; Cheng, Gui-Juan; Liu, Peng; Leow, Dasheng; Sun, Tian-Yu; Chen, Ping; Zhang, Xinhao; Yu, Jin-Quan; Wu, Yun-Dong; Houk, K N

    2014-01-08

    Density functional theory investigations have elucidated the mechanism and origins of meta-regioselectivity of Pd(II)-catalyzed C-H olefinations of toluene derivatives that employ a nitrile-containing template. The reaction proceeds through four major steps: C-H activation, alkene insertion, β-hydride elimination, and reductive elimination. The C-H activation step, which proceeds via a concerted metalation-deprotonation (CMD) pathway, is found to be the rate- and regioselectivity-determining step. For the crucial C-H activation, four possible active catalytic species-monomeric Pd(OAc)2, dimeric Pd2(OAc)4, heterodimeric PdAg(OAc)3, and trimeric Pd3(OAc)6-have been investigated. The computations indicated that the C-H activation with the nitrile-containing template occurs via a Pd-Ag heterodimeric transition state. The nitrile directing group coordinates with Ag while the Pd is placed adjacent to the meta-C-H bond in the transition state, leading to the observed high meta-selectivity. The Pd2(OAc)4 dimeric mechanism also leads to the meta-C-H activation product but with higher activation energies than the Pd-Ag heterodimeric mechanism. The Pd monomeric and trimeric mechanisms require much higher activation free energies and are predicted to give ortho products. Structural and distortion energy analysis of the transition states revealed significant effects of distortions of the template on mechanism and regioselectivity, which provided hints for further developments of new templates.

  6. Transition Metal Free C-N Bond Forming Dearomatizations and Aryl C-H Aminations by in Situ Release of a Hydroxylamine-Based Aminating Agent.

    Science.gov (United States)

    Farndon, Joshua J; Ma, Xiaofeng; Bower, John F

    2017-10-11

    We outline a simple protocol that accesses directly unprotected secondary amines by intramolecular C-N bond forming dearomatization or aryl C-H amination. The method is dependent on the generation of a potent electrophilic aminating agent released by in situ deprotection of O-Ts activated N-Boc hydroxylamines.

  7. Infrared and Raman spectroscopy and quantum chemistry calculation studies of C-H...O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate

    Czech Academy of Sciences Publication Activity Database

    Sato, H.; Dybal, Jiří; Murakami, R.; Noda, I.; Ozaki, Y.

    744-747, - (2005), s. 35-46 ISSN 0022-2860 R&D Projects: GA AV ČR IAA4050208 Keywords : infrared and Raman spectroscopy * quantum chemical calculation * C-H...O hydrogen bonding Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.440, year: 2005

  8. Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

    Science.gov (United States)

    Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

    2018-05-08

    A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Heterometallic Pd(II)-Ni(II) complexes with meso-substituted dibenzotetraaza[14]annulene: double C-H bond activation and formation of a rectangular tetradibenzotetraaza[14]annulene.

    Science.gov (United States)

    Khaledi, Hamid; Olmstead, Marilyn M; Fukuda, Takamitsu; Ali, Hapipah Mohd

    2014-11-03

    Three isomeric 2[Pd(II)-Ni(II)] metal complexes, derived from indoleninyl meso-substituted dibenzotetraaza[14]annulene, were synthesized. The resulting dimers feature Ni···Ni or, alternatively, Ni···π interactions in staggered or slipped cofacial structures. A remarkable insertion of palladium into two different C-H bonds yielded a 4[Pd(II)-Ni(II)] rectangular complex with dimensions of 8.73 × 10.38 Å.

  10. Iodine-catalyzed sp³ C-H bond activation by selenium dioxide: synthesis of diindolylmethanes and di(3-indolyl)selanides.

    Science.gov (United States)

    Naidu, P Seetham; Majumder, Swarup; Bhuyan, Pulak J

    2015-11-01

    An efficient reaction protocol was developed for the synthesis of several diindolylmethane derivatives via the [Formula: see text] C-H bond activation of aryl methyl ketones by [Formula: see text] and indoles in the presence of catalytic amounts of [Formula: see text] at 80 [Formula: see text] using dioxane as solvent. Unexpectedly, an interesting class of di(3-indolyl)selenide compounds was isolated when the reaction was carried out at room temperature.

  11. Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

    Science.gov (United States)

    Zhou, Tian

    Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

  12. Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation.

    Science.gov (United States)

    Ansari, Azaj; Ansari, Mursaleem; Singha, Asmita; Rajaraman, Gopalan

    2017-07-26

    Activation of inert C-H bonds such as those of methane are extremely challenging for chemists but in nature, the soluble methane monooxygenase (sMMO) enzyme readily oxidizes methane to methanol by using a diiron(IV) species. This has prompted chemists to look for similar model systems. Recently, a (μ-oxo)bis(μ-carboxamido)diiron(IV) ([Fe IV 2 O(L) 2 ] 2+ L=N,N-bis-(3',5'-dimethyl-4'-methoxypyridyl-2'-methyl)-N'-acetyl-1,2-diaminoethane) complex has been generated by bulk electrolysis and this species activates inert C-H bonds almost 1000 times faster than mononuclear Fe IV =O species and at the same time selectively activates O-H bonds of alcohols. The very high reactivity and selectivity of this species is puzzling and herein we use extensive DFT calculations to shed light on this aspect. We have studied the electronic and spectral features of diiron {Fe III -μ(O)-Fe III } +2 (complex I), {Fe III -μ(O)-Fe IV } +3 (II), and {Fe IV -μ(O)-Fe IV } +4 (III) complexes. Strong antiferromagnetic coupling between the Fe centers leads to spin-coupled S=0, S=3/2, and S=0 ground state for species I-III respectively. The mechanistic study of the C-H and O-H bond activation reveals a multistate reactivity scenario where C-H bond activation is found to occur through the S=4 spin-coupled state corresponding to the high-spin state of individual Fe IV centers. The O-H bond activation on the other hand, occurs through the S=2 spin-coupled state corresponding to an intermediate state of individual Fe IV centers. Molecular orbital analysis reveals σ-π/π-π channels for the reactivity. The nature of the magnetic exchange interaction is found to be switched during the course of the reaction and this offers lower energy pathways. Significant electronic cooperativity between two metal centers during the course of the reaction has been witnessed and this uncovers the reason behind the efficiency and selectivity observed. The catalyst is found to prudently choose the desired spin

  13. Access to the meta position of arenes through transition metal catalysed C-H bond functionalisation: a focus on metals other than palladium.

    Science.gov (United States)

    Mihai, Madalina T; Genov, Georgi R; Phipps, Robert J

    2018-01-02

    The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play in all manner of important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis in the range of methodologies that are available to elaborate arene C-H bonds. Regioselectivity is an important consideration when selecting a method and, of all those available, it is arguably those that target the meta position that are fewest in number. The rapid development of transition metal-catalysed C-H bond functionalisation over the last few decades has opened new possibilities for meta-selective C-H functionalisation through the diverse reactivity of transition metals and their compatibility with a wide range of directing groups. The pace of discovery of such processes has grown rapidly in the last five years in particular and it is the purpose of this review to examine these but in doing so to place the focus on metals other than palladium, the specific contributions of which have been very recently reviewed elsewhere. It is hoped this will serve to highlight to the reader the breadth of current strategies and mechanisms that have been used to tackle this challenge, which may inspire further progress in the field.

  14. Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step.

    Science.gov (United States)

    Jayakumar, Jayachandran; Cheng, Chien-Hong

    2016-01-26

    A one-pot reaction of substituted benzaldehydes with alkyne-amines by a Rh-catalyzed C-H activation and annulation to afford various natural and unnatural protoberberine alkaloids is reported. This reaction provides a convenient route for the generation of a compound library of protoberberine salts, which recently have attracted great attention because of their diverse biological activities. In addition, pyridinium salt derivatives can also be formed in good yields from α,β-unsaturated aldehydes and amino-alkynes. This reaction proceeds with excellent regioselectivity and good functional group compatibility under mild reaction conditions by using O2 as the oxidant. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Performance of quantum Monte Carlo for calculating molecular bond lengths

    Energy Technology Data Exchange (ETDEWEB)

    Cleland, Deidre M., E-mail: deidre.cleland@csiro.au; Per, Manolo C., E-mail: manolo.per@csiro.au [CSIRO Virtual Nanoscience Laboratory, 343 Royal Parade, Parkville, Victoria 3052 (Australia)

    2016-03-28

    This work investigates the accuracy of real-space quantum Monte Carlo (QMC) methods for calculating molecular geometries. We present the equilibrium bond lengths of a test set of 30 diatomic molecules calculated using variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) methods. The effect of different trial wavefunctions is investigated using single determinants constructed from Hartree-Fock (HF) and Density Functional Theory (DFT) orbitals with LDA, PBE, and B3LYP functionals, as well as small multi-configurational self-consistent field (MCSCF) multi-determinant expansions. When compared to experimental geometries, all DMC methods exhibit smaller mean-absolute deviations (MADs) than those given by HF, DFT, and MCSCF. The most accurate MAD of 3 ± 2 × 10{sup −3} Å is achieved using DMC with a small multi-determinant expansion. However, the more computationally efficient multi-determinant VMC method has a similar MAD of only 4.0 ± 0.9 × 10{sup −3} Å, suggesting that QMC forces calculated from the relatively simple VMC algorithm may often be sufficient for accurate molecular geometries.

  16. Synthesis of Fischer carbene complexes of iridium by C-H bond activation of methyl and cyclic ethers: Evidence for reversible {alpha}-hydrogen migration

    Energy Technology Data Exchange (ETDEWEB)

    Luecke, H.F.; Arndtsen, B.A.; Burger, P.; Bergman, R.G. [Lawrence Berkeley Lab., CA (United States)]|[Univ. of California, Berkeley, CA (United States)

    1996-03-13

    We report here a mild and versatile route to Fischer carbene complexes of iridium via the activation of C-H bonds of methyl and cyclic ethers, along with our preliminary studies of this rare family of carbene complexes. Theoretical studies suggest that {alpha}-hydrogen migrations can be kinetically favorable if a coordinatively unsaturated species can be accessed. Thus, the lability of the triflate ligand presumably facilitates this process. Further evidence for the rapidity, as well as reversibility, of this rearrangement was obtained by NMR analysis. 20 refs.

  17. Ruthenium(II)-catalyzed synthesis of pyrrole- and indole-fused isocoumarins by C-H bond activation in DMF and water

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Sawant, S.G.; Dixneuf, P.H.

    stream_size 26907 stream_content_type text/plain stream_name ChemCatChem_8_1046a.pdf.txt stream_source_info ChemCatChem_8_1046a.pdf.txt Content-Encoding UTF-8 Content-Type text/plain; charset=UTF-8 Author version...: ChemCatChem, vol.8(6); 2016; 1046-1050 Ruthenium(II) catalysed synthesis of pyrrole and indole fused isocoumarins via C-H bond activation in DMF and water† Keisham S. Singh*,a Sneha G. Sawanta, Pierre H. Dixneuf*,b Abstract: Pyrrole and indole...

  18. Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions.

    Science.gov (United States)

    Cui, Li-Qian; Liu, Kai; Zhang, Chi

    2011-04-07

    Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu(4)NHSO(4) could be applied to the effective oxidation of alkanes as well.

  19. Monte Carlo simulation of AB-copolymers with saturating bonds

    CERN Document Server

    Chertovich, A V; Khokhlov, A R; Bohr, J

    2003-01-01

    Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A-and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending on the nature of a particular AB-sequence: statistical random sequence, diblock sequence and 'random-complementary' sequence (one-half of such an AB-sequence is random with Bernoulli statistics while the other half is complementary to the first one). The properties of random-complementary sequences are closer to those of diblock sequences than to the properties of random sequences. The model (although quite rough) is expected to represent some basic features of real RNA molecules, i.e. the formation of secondary structure of RNA due to hydrogen bonding of corresponding bases and stacking interactions of the base pairs in helixes. We introduce the notation of RNA-like copolymers and discuss in what sense the sequences studie...

  20. π-Stacking, C-H/π, and halogen bonding interactions in bromobenzene and mixed bromobenzene-benzene clusters.

    Science.gov (United States)

    Reid, Scott A; Nyambo, Silver; Muzangwa, Lloyd; Uhler, Brandon

    2013-12-19

    Noncovalent interactions play an important role in many chemical and biochemical processes. Building upon our recent study of the homoclusters of chlorobenzene, where π-π stacking and CH/π interactions were identified as the most important binding motifs, in this work we present a study of bromobenzene (PhBr) and mixed bromobenzene-benzene clusters. Electronic spectra in the region of the PhBr monomer S0-S1 (ππ*) transition were obtained using resonant two-photon ionization (R2PI) methods combined with time-of-flight mass analysis. As previously found for related systems, the PhBr cluster spectra show a broad feature whose center is red-shifted from the monomer absorption, and electronic structure calculations indicate the presence of multiple isomers and Franck-Condon activity in low-frequency intermolecular modes. Calculations at the M06-2X/aug-cc-pVDZ level find in total eight minimum energy structures for the PhBr dimer: four π-stacked structures differing in the relative orientation of the Br atoms (denoted D1-D4), one T-shaped structure (D5), and three halogen bonded structures (D6-D8). The calculated binding energies of these complexes, corrected for basis set superposition error (BSSE) and zero-point energy (ZPE), are in the range of -6 to -24 kJ/mol. Time-dependent density functional theory (TDDFT) calculations predict that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectrum. To examine the influence of dipole-dipole interaction, R2PI spectra were also obtained for the mixed PhBr···benzene dimer, where the spectral congestion is reduced and clear vibrational structure is observed. This structure is well-simulated by Franck-Condon calculations that incorporate the lowest frequency intermolecular modes. Calculations find four minimum energy structures for the mixed dimer and predict that the binding energy of the global minimum is reduced by ~30% relative to the global minimum PhBr dimer

  1. Mo-Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond Cleavages Because of the Polarized Electronic Structure in Transition State.

    Science.gov (United States)

    Chen, Yue; Sakaki, Shigeyoshi

    2017-04-03

    The recently reported high reactivity of the Mo-Mo quintuple bond of Mo 2 (N ∧ N) 2 (1) {N ∧ N = μ-κ 2 -CH[N(2,6-iPr 2 C 6 H 3 )] 2 } in the H-H σ-bond cleavage was investigated. DFT calculations disclosed that the H-H σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis-trans isomerization to form the trans-dihydride product, which is consistent with the experimental result. The O-H and C-H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG° ⧧ = 9.0 kcal/mol) and acceptable activation energies (ΔG° ⧧ = 22.5 kcal/mol), respectively, suggesting that the Mo-Mo quintuple bond can be applied to various σ-bond cleavages. In these σ-bond cleavage reactions, the charge-transfer (CT Mo→XH ) from the Mo-Mo quintuple bond to the X-H (X = H, C, or O) bond and that (CT XH→Mo ) from the X-H bond to the Mo-Mo bond play crucial roles. Though the HOMO (dδ-MO) of 1 is at lower energy and the LUMO + 2 (dδ*-MO) of 1 is at higher energy than those of RhCl(PMe 3 ) 2 (LUMO and LUMO + 1 of 1 are not frontier MO), the H-H σ-bond cleavage by 1 more easily occurs than that by the Rh complex. Hence, the frontier MO energies are not the reason for the high reactivity of 1. The high reactivity of 1 arises from the polarization of dδ-type MOs of the Mo-Mo quintuple bond in the transition state. Such a polarized electronic structure enhances the bonding overlap between the dδ-MO of the Mo-Mo bond and the σ*-antibonding MO of the X-H bond to facilitate the CT Mo→XH and reduce the exchange repulsion between the Mo-Mo bond and the X-H bond. This polarized electronic structure of the transition state is similar to that of a frustrated Lewis pair. The easy polarization of the dδ-type MOs is one of the advantages of the metal-metal multiple bond, because such polarization is impossible in the mononuclear metal complex.

  2. Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C-H Bonds

    Science.gov (United States)

    Nadres, Enrico T.; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs

    2013-01-01

    The scope of palladium-catalyzed, auxiliary-assisted direct arylation and alkylation of sp2 and sp3 C-H bonds of amine and carboxylic acid derivatives has been investigated. The method employs a palladium acetate catalyst, substrate, aryl, alkyl, benzyl, or allyl halide, and inorganic base in t-amyl alcohol or water solvent at 100-140 °C. Aryl and alkyl iodides as well as benzyl and allyl bromides are competent reagents in this transformation. Picolinic acid auxiliary is used for amine γ-functionalization and 8-aminoquinoline auxiliary is used for carboxylic acid β-functionalization. Some optimization of base, additives, and solvent is required for achieving best results. PMID:24090404

  3. Rhodium-catalyzed C-H bond activation for the synthesis of quinonoid compounds: Significant Anti-Trypanosoma cruzi activities and electrochemical studies of functionalized quinones.

    Science.gov (United States)

    Jardim, Guilherme A M; Silva, Thaissa L; Goulart, Marilia O F; de Simone, Carlos A; Barbosa, Juliana M C; Salomão, Kelly; de Castro, Solange L; Bower, John F; da Silva Júnior, Eufrânio N

    2017-08-18

    Thirty four halogen and selenium-containing quinones, synthesized by rhodium-catalyzed C-H bond activation and palladium-catalyzed cross-coupling reactions, were evaluated against bloodstream trypomastigotes of T. cruzi. We have identified fifteen compounds with IC 50 /24 h values of less than 2 μM. Electrochemical studies on A-ring functionalized naphthoquinones were also performed aiming to correlate redox properties with trypanocidal activity. For instance, (E)-5-styryl-1,4-naphthoquinone 59 and 5,8-diiodo-1,4-naphthoquinone 3, which are around fifty fold more active than the standard drug benznidazole, are potential derivatives for further investigation. These compounds represent powerful new agents useful in Chagas disease therapy. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  4. Reactivity of the parent amido complexes of iridium with olefins: C-NH2 bond formation versus C-H activation.

    Science.gov (United States)

    Mena, Inmaculada; García-Orduña, Pilar; Polo, Víctor; Lahoz, Fernando J; Casado, Miguel A; Oro, Luis A

    2017-08-29

    Herein we report on the different chemical reactivity displayed by two mononuclear terminal amido compounds depending on the nature of the coordinated diene. Hence, treatment of amido-bridged iridium complexes [{Ir(μ-NH 2 )(tfbb)} 3 ] (1; tfbb = tetrafluorobenzobarrelene) with dppp (dppp = bis(diphenylphosphane)propane) leads to the rupture of the amido bridges forming the mononuclear terminal amido compound [Ir(NH 2 )(dppp)(tfbb)] (3) in the first stage. On changing the reaction conditions, the formation of a C-NH 2 bond between the amido moiety and the coordinated diene is observed and a new dinuclear complex [{Ir(1,2-η 2 -4-κ-C 12 H 8 F 4 N)(dppp)} 2 (μ-dppp)] (4) has been isolated. On the contrary, the diiridium amido-bridged complex [{Ir(μ-NH 2 )(cod)} 2 ] (2; cod = 1,5-cyclooctadiene) in the presence of dppb (dppb = bis(diphenylphosphane)butane) allows the isolation of a mononuclear complex [Ir(1,2,3-η 3 -6-κ-C 8 H 10 )H(dppb)] (5), as a consequence of the extrusion of ammonia. The monitoring of the reaction of 2 with dppb (and dppp) allowed us to detect terminal amido complexes [Ir(NH 2 )(P-P)(cod)] (P-P = dppb (6), dppp (7)) in solution, as confirmed by an X-ray analysis of 7. Complex 7 was observed to evolve into hydrido species 5 at room temperature. DFT studies showed that C-H bond activation occurs through the deprotonation of one methylene fragment of the cod ligand by the highly basic terminal amido moiety instead of C-H oxidative addition to the Ir(i) center.

  5. Gas-phase reactivity of lanthanide cations with fluorocarbons: C-F versus C-H and C-C bond activation

    International Nuclear Information System (INIS)

    Cornehl, H.H.; Hornung, G.; Schwarz, H.

    1996-01-01

    The gas-phase reactivity of the fluorinated hydrocarbons CF 4 , CHF 3 , CH 3 F, C 2 F 6 , 1,1-C 2 H 4 F 2 , and C 6 F 6 with the lanthanide cations Ce + , Pr + , Sm + , Ho + , Tm + , and Yb + and the reactivity of C 6 H 5 F with all lanthanide cations Ln + (Ln = La-Lu, with the exception of Pm + ) have been examined by Fourier-transform ion cyclotron resonance mass spectrometry. The perfluorinated compounds tetrafluoromethane and hexafluoroethane as well as trifluoromethane do not react with any lanthanide cation. Selective activation of the strong C-F bonds in fluoromethane, 1,1-difluoroethane, hexafluorobenzene, and fluorobenzene appears as a general reaction scheme along the 4f row. Experimental evidence is given for a 'harpoon'-like mechanism for the F atom abstraction process which operates via an initial electron transfer from the lanthanide cation to the fluorinated substrate in the encounter complex Ln + RF. The most reactive lanthanides La + , Ce + , Gd + , and Tb + and also the formal closed-shell species Lu + exhibit additional C-H and C-C bond activation pathways in the reaction with fluorobenzene, namely dehydrohalogenation as well as loss of a neutral acetylene molecule. In the case of Tm + and Yb + the formation of neutral LnF 3 is observed in a multistep process via C-C coupling and charge transfer. 17 refs., 2 figs., 2 tabs

  6. Temperature-dependent transitions between normal and inverse isotope effects pertaining to the interaction of H-H and C-H bonds with transition metal centers.

    Science.gov (United States)

    Parkin, Gerard

    2009-02-17

    Deuterium kinetic isotope effects (KIEs) serve as versatile tools to infer details about reaction mechanisms and the nature of transition states, while equilibrium isotope effects (EIEs) associated with the site preferences of hydrogen and deuterium enable researchers to study aspects of molecular structure. Researchers typically interpret primary deuterium isotope effects based on two simple guidelines: (i) the KIE for an elementary reaction is normal (k(H)/k(D) > 1) and (ii) the EIE is dictated by deuterium preferring to be located in the site corresponding to the highest frequency oscillator. In this Account, we evaluate the applicability of these rules to the interactions of H-H and C-H bonds with a transition metal center. Significantly, experimental and computational studies question the predictability of primary EIEs in these systems based on the notion that deuterium prefers to occupy the highest frequency oscillator. In particular, the EIEs for (i) formation of sigma-complexes by coordination of H-H and C-H bonds and (ii) oxidative addition of dihydrogen exhibit unusual temperature dependencies, such that the same system may demonstrate both normal (i.e., K(H)/K(D) > 1) and inverse (i.e., K(H)/K(D) ZPE (where SYM is the symmetry factor, MMI is the mass-moment of inertia term, EXC is the excitation term, and ZPE is the zero-point energy term), and the distinctive temperature profile results from the inverse ZPE (enthalpy) and normal [SYM x MMI x EXC] (entropy) components opposing each other and having different temperature dependencies. At low temperatures, the ZPE component dominates and the EIE is inverse, while at high temperatures, the [SYM x MMI x EXC] component dominates and the EIE is normal. The inverse nature of the ZPE term is a consequence of the rotational and translational degrees of freedom of RH (R = H, CH(3)) becoming low-energy isotopically sensitive vibrations in the product, while the normal nature of the [SYM x MMI x EXC] component

  7. Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

    Science.gov (United States)

    Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

    2010-01-04

    The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

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

    Science.gov (United States)

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

    2010-05-17

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

  9. Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

    Science.gov (United States)

    Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting

    2015-06-28

    Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

  10. Reactive carbon-chain molecules: synthesis of 1-diazo-2,4-pentadiyne and spectroscopic characterization of triplet pentadiynylidene (H-C[triple bond]C-:C-C[triple bond]C-H).

    Science.gov (United States)

    Bowling, Nathan P; Halter, Robert J; Hodges, Jonathan A; Seburg, Randal A; Thomas, Phillip S; Simmons, Christopher S; Stanton, John F; McMahon, Robert J

    2006-03-15

    1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C[triple bond]C-:C-C[triple bond]C-H). Theory predicts an axially symmetric (D(infinity h)) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (absolute value(D/hc) = 0.6157 cm(-1), absolute value(E/hc) = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O2-doped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

  11. Rh(III)-Catalyzed Synthesis of N-Unprotected Indoles from Imidamides and Diazo Ketoesters via C-H Activation and C-C/C-N Bond Cleavage.

    Science.gov (United States)

    Qi, Zisong; Yu, Songjie; Li, Xingwei

    2016-02-19

    The synthesis of N-unprotected indoles has been realized via Rh(III)-catalyzed C-H activation/annulation of imidamides with α-diazo β-ketoesters. The reaction occurs with the release of an amide coproduct, which originates from both the imidamide and the diazo as a result of C═N cleavage of the imidamide and C-C(acyl) cleavage of the diazo. A rhodacyclic intermediate has been isolated and a plausible mechanism has been proposed.

  12. Mechanism of C-C and C-H bond cleavage in ethanol oxidation reaction on Cu2O(111): a DFT-D and DFT+U study.

    Science.gov (United States)

    Xu, Han; Miao, Bei; Zhang, Minhua; Chen, Yifei; Wang, Lichang

    2017-10-04

    The performance of transition metal catalysts for ethanol oxidation reaction (EOR) in direct ethanol fuel cells (DEFCs) may be greatly affected by their oxidation. However, the specific effect and catalytic mechanism for EOR of transition metal oxides are still unclear and deserve in-depth exploitation. Copper as a potential anode catalyst can be easily oxidized in air. Thus, in this study, we investigated C-C and C-H bond cleavage reactions of CH x CO (x = 1, 2, 3) species in EOR on Cu 2 O(111) using PBE+U calculations, as well as the specific effect of +U correction on the process of adsorption and reaction on Cu 2 O(111). It was revealed that the catalytic performance of Cu 2 O(111) for EOR was restrained compared with that of Cu(100). Except for the C-H cleavage of CH 2 CO, all the reaction barriers for C-C and C-H cleavage were higher than those on Cu(100). The most probable pathway for CH 3 CO to CHCO on Cu 2 O(111) was the continuous dehydrogenation reaction. Besides, the barrier for C-C bond cleavage increased due to the loss of H atoms in the intermediate. Moreover, by the comparison of the traditional GGA/PBE method and the PBE+U method, it could be concluded that C-C cleavage barriers would be underestimated without +U correction, while C-H cleavage barriers would be overestimated. +U correction was proved to be necessary, and the reaction barriers and the values of the Hubbard U parameter had a proper linear relationship.

  13. Long range order and hydrogen bonding in liquid methanol: A Monte Carlo simulation

    Energy Technology Data Exchange (ETDEWEB)

    Shilov, I.Y.; Rode, B.M. [Department of Theoretical Chemistry, Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck (Austria); Durov, V.A. [Department of Physical Chemistry, Faculty of Chemistry, Lomonosov Moscow State University, Moscow (Russian Federation)

    1999-02-01

    A Monte Carlo simulation of liquid methanol was performed in NVT ensemble at 298 K using a cubic simulation box containing 500 molecules. Long-range correlations in the liquid are discussed on the basis of site-site radial distribution functions. Hydrogen bonding and topological structure of the methanol aggregates were evaluated in detail, namely the number of linked molecules, formation of branches and cyclic structures. The necessity of larger simulation boxes for a full structural description and thermodynamic characterization of hydrogen-bonded liquids is clearly established by the results. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  14. Orbital interactions and charge redistribution in weak hydrogen bonds: Watson-Crick GC mimic involving C-H proton donor and F proton acceptor groups

    NARCIS (Netherlands)

    Fonseca Guerra, C.; Baerends, E.J.; Bickelhaupt, F.M.

    2006-01-01

    The discovery by Kool and coworkers that 2,4-difluorotoluene (F) mimics thymine (T) in DNA replication has led to controversy regarding the question of whether this mimic has the capability of forming hydrogen bonds with adenine (A). Recently, we have provided evidence for an important role of both

  15. Intermolecular interactions involving C-H bonds, 3, Structure and energetics of the interaction between CH{sub 4} and CN{sup {minus}}

    Energy Technology Data Exchange (ETDEWEB)

    Novoa, J.J.; Whangbo, Myung-Hwan [North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry; Williams, J.M. [Argonne National Lab., IL (United States)

    1991-12-31

    On the basis of SCF and single reference MP2 calculations, the full potential energy surface of the interaction between CH{sub 4} and CN{sup {minus}} was studied using extended basis sets of up to near Hartree-Fock limit quality. Colinear arrangements C-N{sup {minus}}{hor_ellipsis}H-CH{sub 3} and N-C{sup {minus}}{hor_ellipsis}H-CH{sub 3} are found to be the only two energy minima. The binding energies of these two structures are calculated to be 2.5 and 2.1 kcal/mol, respectively, at the MP2 level. The full vibrational analyses of two structures show a red shift of about 30 cm{sup {minus}1} for the v{sub s} C-H stretching.

  16. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve......-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  17. A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

    Science.gov (United States)

    Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

    2017-11-01

    The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

  18. Electronic Effects on Room-Temperature, Gas-Phase C-H Bond Activations by Cluster Oxides and Metal Carbides: The Methane Challenge.

    Science.gov (United States)

    Schwarz, Helmut; Shaik, Sason; Li, Jilai

    2017-12-06

    This Perspective discusses a story of one molecule (methane), a few metal-oxide cationic clusters (MOCCs), dopants, metal-carbide cations, oriented-electric fields (OEFs), and a dizzying mechanistic landscape of methane activation! One mechanism is hydrogen atom transfer (HAT), which occurs whenever the MOCC possesses a localized oxyl radical (M-O • ). Whenever the radical is delocalized, e.g., in [MgO] n •+ the HAT barrier increases due to the penalty of radical localization. Adding a dopant (Ga 2 O 3 ) to [MgO] 2 •+ localizes the radical and HAT transpires. Whenever the radical is located on the metal centers as in [Al 2 O 2 ] •+ the mechanism crosses over to proton-coupled electron transfer (PCET), wherein the positive Al center acts as a Lewis acid that coordinates the methane molecule, while one of the bridging oxygen atoms abstracts a proton, and the negatively charged CH 3 moiety relocates to the metal fragment. We provide a diagnostic plot of barriers vs reactants' distortion energies, which allows the chemist to distinguish HAT from PCET. Thus, doping of [MgO] 2 •+ by Al 2 O 3 enables HAT and PCET to compete. Similarly, [ZnO] •+ activates methane by PCET generating many products. Adding a CH 3 CN ligand to form [(CH 3 CN)ZnO] •+ leads to a single HAT product. The CH 3 CN dipole acts as an OEF that switches off PCET. [MC] + cations (M = Au, Cu) act by different mechanisms, dictated by the M + -C bond covalence. For example, Cu + , which bonds the carbon atom mostly electrostatically, performs coupling of C to methane to yield ethylene, in a single almost barrier-free step, with an unprecedented atomic choreography catalyzed by the OEF of Cu + .

  19. α 'agostic' assistance in Ziegler-Natta polymerization of olefins. Deuterium isotopic perturbation of stereochemistry indicating coordination of an α C-H bond in chain propagation

    International Nuclear Information System (INIS)

    Piers, W.E.; Bercaw, J.E.

    1990-01-01

    The well-defined, homogeneous Ziegler-Natta olefin polymerization systems that have been reported recently provide an unprecedented opportunity to investigate the mechanism of this important process. While a consensus appears to be developing that in all these systems the active catalysts are the 14-electron, d 0 (or d 0 f n ) metallocene alkyls, Cp 2 MR (M = lanthanide or group 3 transition metal) or [Cp 2 MR] + (M = group 4 transition metal), the mechanism for chain propagation and the geometry of the transition state for olefin insertion into the metal-carbon bond have not yet been unequivocally established. In a cleverly conceived experiment, Grubbs et al. probed for an α agostic interaction in the transition state for olefin insertion. Racemic 1-d 1 -5-hexenylchlorotitanocene was prepared and found to undergo AlCl 2 (CH 2 CH 3 )-induced cyclization to a mixture of cis- and trans-2-d 1 -cyclopentylmethyl stereoisomers. Any α agostic assistance in the insertion step is expected to favor the trans product (vide infra). Hydrolysis and 2 H NMR analysis of the resultant mixture of deuteriomethylcyclopentanes revealed a 1.00 ± 0.05 ratio of trans:cis products, arguing against an α agostic assisted insertion in their system, however. The scandium hydride, {(η 5 -C 5 Me 4 ) 2 SiMe 2 }Sc(PMe 3 )H ('OpSc(PMe 3 )H'), cleanly catalyzes the hydrocyclization of 1,5-hexadiene to methylcyclopentane. The authors have adapted this catalytic hydrocyclization reaction along the lines of the Grubbs experiment to probe for α agostic assistance with the scandium system

  20. Electrochemical Cobalt-Catalyzed C-H Activation.

    Science.gov (United States)

    Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

    2018-06-19

    Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The labeling of unsaturated gamma-hydroxybutyric acid by heavy isotopes of hydrogen: iridium complex-mediated H/D exchange by C-H bond activation vs reduction by boro-deuterides/tritides

    Czech Academy of Sciences Publication Activity Database

    Marek, Aleš; Pedersen, M. H. F.; Vogensen, S. B.; Clausen, R. P.; Frolund, B.; Elbert, Tomáš

    2016-01-01

    Roč. 59, č. 12 (2016), s. 476-483 ISSN 0362-4803 Institutional support: RVO:61388963 Keywords : C-H activation * borotritides * hydrogen/deuterium exchange * iridium catalyst * tritium-labeled gamma-hydroxybutyric acid Subject RIV: CC - Organic Chemistry Impact factor: 1.745, year: 2016

  2. Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination.

    Science.gov (United States)

    Hyster, Todd K; Farwell, Christopher C; Buller, Andrew R; McIntosh, John A; Arnold, Frances H

    2014-11-05

    We recently demonstrated that variants of cytochrome P450BM3 (CYP102A1) catalyze the insertion of nitrogen species into benzylic C-H bonds to form new C-N bonds. An outstanding challenge in the field of C-H amination is catalyst-controlled regioselectivity. Here, we report two engineered variants of P450BM3 that provide divergent regioselectivity for C-H amination-one favoring amination of benzylic C-H bonds and the other favoring homo-benzylic C-H bonds. The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that C-H abstraction is rate-limiting. The 2.66-Å crystal structure of the most active enzyme suggests that the engineered active site can preorganize the substrate for reactivity. We hypothesize that the enzyme controls regioselectivity through localization of a single C-H bond close to the iron nitrenoid.

  3. Conformation-induced remote meta-C-H activation of amines

    Science.gov (United States)

    Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan

    2014-03-01

    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a long-standing challenge in organic chemistry. The small differences in intrinsic reactivity of C-H bonds in any given organic molecule can lead to the activation of undesired C-H bonds by a non-selective catalyst. One solution to this problem is to distinguish C-H bonds on the basis of their location in the molecule relative to a specific functional group. In this context, the activation of C-H bonds five or six bonds away from a functional group by cyclometallation has been extensively studied. However, the directed activation of C-H bonds that are distal to (more than six bonds away) functional groups has remained challenging, especially when the target C-H bond is geometrically inaccessible to directed metallation owing to the ring strain encountered in cyclometallation. Here we report a recyclable template that directs the olefination and acetoxylation of distal meta-C-H bonds--as far as 11 bonds away--of anilines and benzylic amines. This template is able to direct the meta-selective C-H functionalization of bicyclic heterocycles via a highly strained, tricyclic-cyclophane-like palladated intermediate. X-ray and nuclear magnetic resonance studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by using a ligand to switch from ortho- to meta-selectivity.

  4. Identification and H(D)-bond energies of C-H(D)Cl interactions in chloride-haloalkane clusters: a combined X-ray crystallographic, spectroscopic, and theoretical study.

    Science.gov (United States)

    Serebryanskaya, Tatiyana V; Novikov, Alexander S; Gushchin, Pavel V; Haukka, Matti; Asfin, Ruslan E; Tolstoy, Peter M; Kukushkin, Vadim Yu

    2016-05-18

    The cationic (1,3,5-triazapentadiene)Pt(II) complex [Pt{NH[double bond, length as m-dash]C(N(CH2)5)N(Ph)C(NH2)[double bond, length as m-dash]NPh}2]Cl2 ([]Cl2) was crystallized from four haloalkane solvents giving [][Cl2(CDCl3)4], [][Cl2(CHBr3)4], [][Cl2(CH2Cl2)2], and [][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [][Cl2(CDCl3)4] and [][Cl2(CHBr3)4], the Cl(-) ion interacts with two haloform molecules via C-DCl(-) and C-HCl(-) contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2](-) and [Cl(CHBr3)2](-). In the structures of [][Cl2(CH2Cl2)2] and [][Cl2(C2H4Cl2)2], cations [](2+) are linked to a 3D-network by a system of H-bondings including one formed by each Cl(-) ion with CH2Cl2 or C2H4Cl2 molecules. The lengths and energies of these H-bonds in the chloride-haloalkane clusters were analyzed by DFT calculations (M06 functional) including AIM analysis. The crystal packing noticeably affected the geometry of the clusters, and energy of C-HCl(-) hydrogen bonds ranged from 1 to 6 kcal mol(-1). An exponential correlation (R(2) > 0.98) between the calculated Cl(-)H distances and the energies of the corresponding contacts was found and used to calculate hydrogen bond energies from the experimental Cl(-)H distances. Predicted energy values (3.3-3.9 kcal mol(-1) for the [Cl(CHCl3)2](-) cluster) are in a reasonable agreement with the energy of the Cl3C-HCl(-) bond estimated using ATRFTIR spectroscopy (2.7 kcal mol(-1)).

  5. Recent Developments in C-H Activation for Materials Science in the Center for Selective C-H Activation.

    Science.gov (United States)

    Zhang, Junxiang; Kang, Lauren J; Parker, Timothy C; Blakey, Simon B; Luscombe, Christine K; Marder, Seth R

    2018-04-16

    Abstract : Organic electronics is a rapidly growing field driven in large part by the synthesis of ∏-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of ∏-conjugated molecules and polymers, but the synthesis of intermediates necessary for traditional cross-couplings can include multiple steps with toxic and hazardous reagents. Direct arylation through C-H bond activation has the potential to reduce the number of steps and hazards while being more atom-economical. Within the Center for Selective C-H Functionalization (CCHF), we have been developing C-H activation methodology for the synthesis of ∏-conjugated materials of interest, including direct arylation of difficult-to-functionalize electron acceptor intermediates and living polymerization of ∏-conjugated polymers through C-H activation.

  6. Ligand-controlled, tunable silver-catalyzed C-H amination.

    Science.gov (United States)

    Alderson, Juliet M; Phelps, Alicia M; Scamp, Ryan J; Dolan, Nicholas S; Schomaker, Jennifer M

    2014-12-03

    The development of readily tunable and regioselective C-H functionalization reactions that operate solely through catalyst control remains a challenge in modern organic synthesis. Herein, we report that simple silver catalysts supported by common nitrogenated ligands can be used to tune a nitrene transfer reaction between two different types of C-H bonds. The results reported herein represent the first example of ligand-controlled and site-selective silver-promoted C-H amination.

  7. Synthesis of propargylic and allenic carbamates via the C-H amination of alkynes.

    Science.gov (United States)

    Grigg, R David; Rigoli, Jared W; Pearce, Simon D; Schomaker, Jennifer M

    2012-01-06

    Propargylic amines are important intermediates for the synthesis of nitrogen-containing heterocycles. The insertion of a nitrene into a propargylic C-H bond has not been explored, despite the attention directed toward the Rh-catalyzed amination of other types of C-H bonds. In this communication, the conversion of a series of homopropargylic carbamates to propargylic carbamates and aminated allenes is described. © 2011 American Chemical Society

  8. Palladium-catalysed electrophilic aromatic C-H fluorination

    Science.gov (United States)

    Yamamoto, Kumiko; Li, Jiakun; Garber, Jeffrey A. O.; Rolfes, Julian D.; Boursalian, Gregory B.; Borghs, Jannik C.; Genicot, Christophe; Jacq, Jérôme; van Gastel, Maurice; Neese, Frank; Ritter, Tobias

    2018-02-01

    Aryl fluorides are widely used in the pharmaceutical and agrochemical industries, and recent advances have enabled their synthesis through the conversion of various functional groups. However, there is a lack of general methods for direct aromatic carbon-hydrogen (C-H) fluorination. Conventional methods require the use of either strong fluorinating reagents, which are often unselective and difficult to handle, such as elemental fluorine, or less reactive reagents that attack only the most activated arenes, which reduces the substrate scope. A method for the direct fluorination of aromatic C-H bonds could facilitate access to fluorinated derivatives of functional molecules that would otherwise be difficult to produce. For example, drug candidates with improved properties, such as increased metabolic stability or better blood-brain-barrier penetration, may become available. Here we describe an approach to catalysis and the resulting development of an undirected, palladium-catalysed method for aromatic C-H fluorination using mild electrophilic fluorinating reagents. The reaction involves a mode of catalysis that is unusual in aromatic C-H functionalization because no organometallic intermediate is formed; instead, a reactive transition-metal-fluoride electrophile is generated catalytically for the fluorination of arenes that do not otherwise react with mild fluorinating reagents. The scope and functional-group tolerance of this reaction could provide access to functional fluorinated molecules in pharmaceutical and agrochemical development that would otherwise not be readily accessible.

  9. Fixed-Node Diffusion Quantum Monte Carlo Method on Dissociation Energies and Their Trends for R-X Bonds (R = Me, Et, i-Pr, t-Bu).

    Science.gov (United States)

    Hou, Aiqiang; Zhou, Xiaojun; Wang, Ting; Wang, Fan

    2018-05-15

    Achieving both bond dissociation energies (BDEs) and their trends for the R-X bonds with R = Me, Et, i-Pr, and t-Bu reliably is nontrivial. Density functional theory (DFT) methods with traditional exchange-correlation functionals usually have large error on both the BDEs and their trends. The M06-2X functional gives rise to reliable BDEs, but the relative BDEs are determined not as accurately. More demanding approaches such as some double-hybrid functionals, for example, G4 and CCSD(T), are generally required to achieve the BDEs and their trends reliably. The fixed-node diffusion quantum Monte Carlo method (FN-DMC) is employed to calculated BDEs of these R-X bonds with X = H, CH 3 , OCH 3 , OH, and F in this work. The single Slater-Jastrow wave function is adopted as trial wave function, and pseudopotentials (PPs) developed for quantum Monte Carlo calculations are chosen. Error of these PPs is modest in wave function methods, while it is more pronounced in DFT calculations. Our results show that accuracy of BDEs with FN-DMC is similar to that of M06-2X and G4, and trends in BDEs are calculated more reliably than M06-2X. Both BDEs and trends in BDEs of these bonds are reproduced reasonably with FN-DMC. FN-DMC using PPs can thus be applied to BDEs and their trends of similar chemical bonds in larger molecules reliably and provide valuable information on properties of these molecules.

  10. Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C

    2017-07-06

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  11. Selective sp3 C-H alkylation via polarity-match-based cross-coupling

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

    2017-07-01

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  12. Rhodium (II) carbene C-H insertion in water and catalyst reuse; Insercao C-H de carbenoides de rodio em agua e reutilizacao do catalisador

    Energy Technology Data Exchange (ETDEWEB)

    Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M. [Instituto Superior Tecnico, Lisboa (Portugal)]. E-mail: carlosafonso@ist.utl.pt

    2007-07-01

    A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh{sub 2}(OAc){sub 4}. The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

  13. Superioridad relativa de los estimadores Kiviet y Blundell-Bond (GMM1 en paneles dinámicos. Un experimento Monte Carlo con muestras finitas

    Directory of Open Access Journals (Sweden)

    Andrés Eduardo Rangel Jiménez

    2012-10-01

    Full Text Available Dado el amplio uso de los datos de panel en modelos dinamicos, es relevante evaluar el desempeno de sus diferentes estimadores en muestras finitas en presencia de baja y alta persistencia. El presente articulo tiene como objetivo analizar, mediante simulaciones tipo Monte Carlo, las propiedades de los estimadores de efectos fijos (LSDV, Arellano y Bond (AB-GMM1, Blundell y Bond (BB-GMM1, Anderson y Hsiao (AH y Kiviet. Se concluye que en series no persistentes el estimador de Kiviet es el de mejor desempeno, basandose en los criterios de error cuadratico medio, sesgo y desviacion estandar; con alta persistencia, el estimador BB-GMM1 es el de mejor desempeno seguido por el estimador de Kiviet, que se comporta bien excepto en micropaneles con series persistentes.

  14. Directing-Group-mediated C-H-Alkynylations.

    Science.gov (United States)

    Caspers, Lucien D; Nachtsheim, Boris J

    2018-05-18

    C-C triple bonds are amongst the most versatile functional groups in synthetic chemistry. Complementary to the Sonogashira coupling the direct metal-catalyzed alkynylation of C-H bonds has emerged as a highly promising approach in recent years. To guarantee a high regioselectivity suitable directing groups (DGs) are necessary to guide the transition metal (TM) into the right place. In this Focus Review we present the current developments in DG-mediated C(sp 2 )-H and C(sp 3 )-H modifications with terminal alkynes under oxidative conditions and with electrophilic alkynylation reagents. We will discuss further modifications of the alkyne, in particular subsequent cyclizations to carbo- and heterocycles and modifications of the DG in the presence of the alkyne. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Rhodium (II) carbene C-H insertion in water and catalyst reuse

    International Nuclear Information System (INIS)

    Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M.

    2007-01-01

    A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh 2 (OAc) 4 . The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

  16. Phenylacetylene and H bond

    Indian Academy of Sciences (India)

    ... all resembling H bonds. Non-linear H bonds due to secondary interactions. C-H stretching frequency shows blue shift. Heavy atom distances are longer than the sum of van der Waals radii. Formed a task group through IUPAC to come up with a modern definition of H bond. 15 international experts including Desiraju.

  17. Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

    Science.gov (United States)

    Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

    2013-12-02

    A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis of heterocyclic compounds through palladium-catalyzed C-H cyclization processes.

    Science.gov (United States)

    Inamoto, Kiyofumi

    2013-01-01

    Herein, we describe our development of synthetic methods for heterocyclic compounds based on the palladium-catalyzed carbon-hydrogen bond (C-H) functionalization/intramolecular carbon-heteroatom (nitrogen or sulfur) bond formation process. By this C-H cyclization method, we efficiently prepared various N-heterocycles, including indazoles, indoles, and 2-quinolinones, as well as S-heterocycles such as benzothiazoles and benzo[b]thiophenes. Yields are typically good to high and good functional-group tolerance is observed for each process, thereby indicating that the method provides a novel, highly applicable synthetic route to the abovementioned biologically important heterocyclic frameworks. As an application of this approach, an auto-tandem-type, one-pot process involving the oxidative Heck reaction and subsequent C-H cyclization using cinnamamides and arylboronic acids as starting materials in the presence of a palladium catalyst was also developed for the rapid construction of the 2-quinolinone nucleus.

  19. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  20. Direct C-H alkylation and indole formation of anilines with diazo compounds under rhodium catalysis.

    Science.gov (United States)

    Mishra, Neeraj Kumar; Choi, Miji; Jo, Hyeim; Oh, Yongguk; Sharma, Satyasheel; Han, Sang Hoon; Jeong, Taejoo; Han, Sangil; Lee, Seok-Yong; Kim, In Su

    2015-12-18

    The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

  1. Deposition and characterisation of multilayer hard coatings. Ti/TiNδ/TiCxNy/(TiC) a-C:H/(Ti) a-C:H

    International Nuclear Information System (INIS)

    Burinprakhon, T.

    2001-02-01

    Multilayer hard coatings containing Ti, TiNδ, TiC x N y , (TiC m ) a-C:H, (TiC n ) a-C:H, and (Ti) a-C:H were deposited on commercially pure titanium substrates by using an asymmetric bipolar pulsed-dc reactive magnetron sputtering of a titanium target, with Ar, Ar+N 2 , Ar+N 2 +CH 4 , and Ar+CH 4 gas mixtures. The microstructures, elemental compositions and bonding states of the interlayers and the coating surfaces were studied by using cross-sectional transmission electron microscopy (XTEM), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The microstructure development of the multilayer coating was strongly influenced by target poisoning. As a result of the complete poisoning of the titanium target during the deposition of TiNδ and TiC x N y interlayers, the a-C:H interlayers containing graded titanium and nitrogen contents were found to develop successively to the TiC x N y interlayer without the formation of near-stoichiometric TiC. The (TiC m ) a-C:H interlayer consisted of nano-particles of distorted fcc crystal structure embedded in the a-C:H matrix. The (TiC n ) a-C:H and (Ti) a-C:H top layers were found to be a-C:H matrix without nano-particles. In the (Ti) a-C:H top layer there was no measurable amount of Ti observed, regardless of the variation of CH 4 concentration between 37.5 and 60 % flow rate in Ar+-CH4 gas mixture. The top layer (Ti) a-C:H was found to contain approximately 10 atomic % nitrogen, due to N 2 contamination during deposition caused by low conductance of N 2 through the nominally closed valve of the mass flow controller. The change of the CH 4 concentration during deposition of the top layer (Ti) a-C:H, however, showed a strong influence on the hydrogen content. The comparison of the fluorescence background of the Raman spectra revealed that hydrogen-less (Ti) a-C:H was deposited at a CH 4 concentration of less than 50 % flow rate in Ar. The hardness

  2. Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts.

    Science.gov (United States)

    Hari, Durga Prasad; Schroll, Peter; König, Burkhard

    2012-02-15

    Visible light along with 1 mol % eosin Y catalyzes the direct C-H bond arylation of heteroarenes with aryl diazonium salts by a photoredox process. We have investigated the scope of the reaction for several aryl diazonium salts and heteroarenes. The general and easy procedure provides a transition-metal-free alternative for the formation of aryl-heteroaryl bonds.

  3. A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate

    Science.gov (United States)

    Kuninobu, Yoichiro; Ida, Haruka; Nishi, Mitsumi; Kanai, Motomu

    2015-09-01

    Regioselective C-H bond transformations are potentially the most efficient method for the synthesis of organic molecules. However, the presence of many C-H bonds in organic molecules and the high activation barrier for these reactions make these transformations difficult. Directing groups in the reaction substrate are often used to control regioselectivity, which has been especially successful for the ortho-selective functionalization of aromatic substrates. Here, we describe an iridium-catalysed meta-selective C-H borylation of aromatic compounds using a newly designed catalytic system. The bipyridine-derived ligand that binds iridium contains a pendant urea moiety. A secondary interaction between this urea and a hydrogen-bond acceptor in the substrate places the iridium in close proximity to the meta-C-H bond and thus controls the regioselectivity. 1H NMR studies and control experiments support the participation of hydrogen bonds in inducing regioselectivity. Reversible direction of the catalyst through hydrogen bonds is a versatile concept for regioselective C-H transformations.

  4. Substrate-Mediated C-C and C-H Coupling after Dehalogenation.

    Science.gov (United States)

    Kong, Huihui; Yang, Sha; Gao, Hongying; Timmer, Alexander; Hill, Jonathan P; Díaz Arado, Oscar; Mönig, Harry; Huang, Xinyan; Tang, Qin; Ji, Qingmin; Liu, Wei; Fuchs, Harald

    2017-03-15

    Intermolecular C-C coupling after cleavage of C-X (mostly, X = Br or I) bonds has been extensively studied for facilitating the synthesis of polymeric nanostructures. However, the accidental appearance of C-H coupling at the terminal carbon atoms would limit the successive extension of covalent polymers. To our knowledge, the selective C-H coupling after dehalogenation has not so far been reported, which may illuminate another interesting field of chemical synthesis on surfaces besides in situ fabrication of polymers, i.e., synthesis of novel organic molecules. By combining STM imaging, XPS analysis, and DFT calculations, we have achieved predominant C-C coupling on Au(111) and more interestingly selective C-H coupling on Ag(111), which in turn leads to selective synthesis of polymeric chains or new organic molecules.

  5. Thermal stability of nanocomposite CrC/a-C:H thin films

    International Nuclear Information System (INIS)

    Gassner, G.; Mayrhofer, P.H.; Patscheider, J.; Mitterer, C.

    2007-01-01

    The thermal stability of low-friction Me-C/a-C:H coatings is important for their potential applications in the tool and automotive industry. Recently we showed that CrC x /a-C:H coatings prepared by unbalanced magnetron sputtering of a Cr target in Ar + CH 4 glow discharges exhibit a nanocomposite structure where metastable fcc CrC nanocrystals are encapsulated by an a-C:H phase. Here, we present the structural evolution of these nanocomposite CrC/a-C:H coatings during annealing. High-temperature X-ray diffraction in vacuum and differential scanning calorimetry (DSC) combined with thermo-gravimetric analysis in Ar atmosphere indicate decomposition of the formed metastable fcc CrC phase and subsequent formation of Cr 3 C 2 and Cr 7 C 3 and structural transformation of the a-C:H matrix phase towards higher sp 2 bonding contents at temperatures above 450 deg. C. Combined DSC and mass spectrometer analysis as well as elemental profiling after annealing in vacuum by elastic recoil detection analysis relate this transformation to the loss of bonded hydrogen at temperatures above 200 deg. C. Due to these structural changes the coefficient of friction depends on the annealing temperature of the nanocomposite a-C:H coatings and shows a minimum of ∼ 0.13 for T = 200 deg. C. The more complex tribochemical reactions, influenced by the hydrogen loss from the coating during in-situ high temperatures ball-on disc tests, result in coefficient of friction values below 0.05 for T < 120 deg. C

  6. Oxidant-free Rh(III)-catalyzed direct C-H olefination of arenes with allyl acetates.

    Science.gov (United States)

    Feng, Chao; Feng, Daming; Loh, Teck-Peng

    2013-07-19

    Rh(III)-catalyzed direct olefination of arenes with allyl acetate via C-H bond activation is described using N,N-disubstituted aminocarbonyl as the directing group. The catalyst undergoes a redox neutral process, and high to excellent yields of trans-products are obtained. This protocol exhibits a wide spectrum of functionality compatibility because of the simple reaction conditions employed and provides a highly effective synthetic method in the realm of C-H olefination.

  7. Ligand-accelerated non-directed C-H functionalization of arenes

    Science.gov (United States)

    Wang, Peng; Verma, Pritha; Xia, Guoqin; Shi, Jun; Qiao, Jennifer X.; Tao, Shiwei; Cheng, Peter T. W.; Poss, Michael A.; Farmer, Marcus E.; Yeung, Kap-Sun; Yu, Jin-Quan

    2017-11-01

    The directed activation of carbon-hydrogen bonds (C-H) is important in the development of synthetically useful reactions, owing to the proximity-induced reactivity and selectivity that is enabled by coordinating functional groups. Palladium-catalysed non-directed C-H activation could potentially enable further useful reactions, because it can reach more distant sites and be applied to substrates that do not contain appropriate directing groups; however, its development has faced substantial challenges associated with the lack of sufficiently active palladium catalysts. Currently used palladium catalysts are reactive only with electron-rich arenes, unless an excess of arene is used, which limits synthetic applications. Here we report a 2-pyridone ligand that binds to palladium and accelerates non-directed C-H functionalization with arene as the limiting reagent. This protocol is compatible with a broad range of aromatic substrates and we demonstrate direct functionalization of advanced synthetic intermediates, drug molecules and natural products that cannot be used in excessive quantities. We also developed C-H olefination and carboxylation protocols, demonstrating the applicability of our methodology to other transformations. The site selectivity in these transformations is governed by a combination of steric and electronic effects, with the pyridone ligand enhancing the influence of sterics on the selectivity, thus providing complementary selectivity to directed C-H functionalization.

  8. Selectivity control in pd-catalyzed c-h functionalization reactions

    OpenAIRE

    Flores Gaspar, Areli

    2013-01-01

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

  9. Carbon dioxide utilization via carbonate-promoted C-H carboxylation.

    Science.gov (United States)

    Banerjee, Aanindeeta; Dick, Graham R; Yoshino, Tatsuhiko; Kanan, Matthew W

    2016-03-10

    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  10. Rhodium(I)-catalyzed cycloisomerization of benzylallene-alkynes through C-H activation.

    Science.gov (United States)

    Kawaguchi, Yasuaki; Yasuda, Shigeo; Kaneko, Akira; Oura, Yuki; Mukai, Chisato

    2014-07-14

    The efficient Rh(I)-catalyzed cycloisomerization of benzylallene-alkynes produced the tricyclo[9.4.0.0(3,8)]pentadecapentaene skeleton through a C(sp2)-H bond activation in good yields. A plausible reaction mechanism proceeds via oxidative addition of the acetylenic C-H bond to Rh(I), an ene-type cyclization to the vinylidenecarbene-Rh(I) intermediate, and an electrophilic aromatic substitution with the vinylidenecarbene species. It was proposed based on deuteration and competition experiments. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Polymeric thermal analysis of C + H and C + H + Ar ion implanted UHMWPE samples

    International Nuclear Information System (INIS)

    Kaya, N.; Oztarhan, Ahmet M.; Urkac, E.S.; Ila, D.; Budak, S.; Oks, E.; Nikolaev, A.; Ezdesir, A.; Tihminlioglu, F.; Tek, Z.; Cetiner, S.; Muntele, C.

    2007-01-01

    Chemical surface characterization of C + H hybrid ion implanted UHMWPE samples were carried out using DSC (differential scanning calorimeter) and TGA (thermal gravimetric analysis) techniques. Samples were implanted with a fluence of 10 17 ion/cm 2 and an extraction voltage of 30 kV. The study of TGA and DSC curves showed that: (1) Polymeric decomposition temperature increased (2) T m , ΔC p and ΔH m values changed while ΔC p and ΔH m increased. T g value could not be measured, because of some experimental limitations. However, the increase in ΔH m values showed that T g values increased (3) the branch density which indicated the increase in number of cross-link (M c ) decreased in ion implanted samples and (4) increase in ΔH m values indicated increase in crystallinity of implanted surface of UHMWPE samples

  12. Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives.

    Science.gov (United States)

    Misal Castro, Luis C; Chatani, Naoto

    2014-04-14

    The palladium-catalyzed arylation/alkylation of ortho-C-H bonds in N-benzoyl α-amino ester derivatives is described. In such a system both the NH-amido and the CO2R groups in the α-amino ester moieties play a role in successful C-H activation/C-C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron-rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Radical Cation Salt-initiated Aerobic C-H Phosphorylation of N-Benzylanilines: Synthesis of a-Aminophosphonates.

    Science.gov (United States)

    Jia, Xiao Dong; Liu, Xiaofei; Yuan, Yu; Li, Pengfei; Hou, Wentao; He, Kaixuan

    2018-06-03

    A radical cation salt-initiated phosphorylation of N-benzylanilines was realized through the aerobic oxidation of sp3 C-H bond, providing a series of α-aminophosphonates in high yields. The investigation of the reaction scope revealed that this mild catalyst system is superior in good functional group tolerance and high reaction efficiency. The mechanistic study implied that the cleavage of the sp3 C-H bond was involved in the rate-determining step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation.

    Science.gov (United States)

    Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz

    2018-04-06

    Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ir-catalyzed C-H silylations of phenyldeazapurines

    Czech Academy of Sciences Publication Activity Database

    Sabat, Nazarii; Poštová Slavětínská, Lenka; Hocek, Michal

    2015-01-01

    Roč. 56, č. 49 (2015), s. 6860-6862 ISSN 0040-4039 Institutional support: RVO:61388963 Keywords : C-H silylation * deazapurines * iridium catalysis * C-H activations Subject RIV: CC - Organic Chemistry Impact factor: 2.347, year: 2015

  16. Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source.

    Science.gov (United States)

    Furusawa, Takuma; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Tanimoto, Hiroki; Kakiuchi, Kiyomi

    2016-08-19

    Synthesis of fluoren-9-ones by a Rh-catalyzed intramolecular C-H/C-I carbonylative coupling of 2-iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate-determining step is not a C-H bond cleavage but, rather, the oxidative addition of the C-I bond to a Rh(I) center. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Oxidative C-H Activation Approach to Pyridone and Isoquinolone through an Iron-Catalyzed Coupling of Amides with Alkynes.

    Science.gov (United States)

    Matsubara, Tatsuaki; Ilies, Laurean; Nakamura, Eiichi

    2016-02-04

    An iron catalyst combined with a mild organic oxidant promotes both C-H bond cleavage and C-N bond formation, and forms 2-pyridones and isoquinolones from an alkene- or arylamide and an internal alkyne, respectively. An unsymmetrical alkyne gives the pyridone derivative with high regioselectivity, this could be due to the sensitivity of the reaction to steric effects because of the compact size of iron. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Radical C-H functionalization to construct heterocyclic compounds.

    Science.gov (United States)

    Yu, Jin-Tao; Pan, Changduo

    2016-02-07

    Heterocyclic compounds are widely present in natural products, pharmaceuticals and bioactive molecules. Thus, organic and pharmaceutical chemists have been making extensive efforts to construct those heterocyclic frameworks through developing versatile and efficient synthetic strategies. The direct C-H functionalization via the radical pathway has emerged as a promising and dramatic approach towards heterocycles with high atom- and step-economy. Heterocyclic compounds such as coumarins, furans, benzofurans, xanthones, benzothiazoles, indoles, indolines, oxindoles, quinolines, isoquinolines, quinoxaline, and phenanthridines have been successfully synthesized by C-H functionalization through the radical pathway. In this review, recent advances on radical C-H functionalization to construct heterocyclic compounds are highlighted with discussions.

  19. Complementation of biotransformations with chemical C-H oxidation: copper-catalyzed oxidation of tertiary amines in complex pharmaceuticals.

    Science.gov (United States)

    Genovino, Julien; Lütz, Stephan; Sames, Dalibor; Touré, B Barry

    2013-08-21

    The isolation, quantitation, and characterization of drug metabolites in biological fluids remain challenging. Rapid access to oxidized drugs could facilitate metabolite identification and enable early pharmacology and toxicity studies. Herein, we compared biotransformations to classical and new chemical C-H oxidation methods using oxcarbazepine, naproxen, and an early compound hit (phthalazine 1). These studies illustrated the low preparative efficacy of biotransformations and the inability of chemical methods to oxidize complex pharmaceuticals. We also disclose an aerobic catalytic protocole (CuI/air) to oxidize tertiary amines and benzylic CH's in drugs. The reaction tolerates a broad range of functionalities and displays a high level of chemoselectivity, which is not generally explained by the strength of the C-H bonds but by the individual structural chemotype. This study represents a first step toward establishing a chemical toolkit (chemotransformations) that can selectively oxidize C-H bonds in complex pharmaceuticals and rapidly deliver drug metabolites.

  20. Sequential meta-C-H olefination of synthetically versatile benzyl silanes: effective synthesis of meta-olefinated toluene, benzaldehyde and benzyl alcohols.

    Science.gov (United States)

    Patra, Tuhin; Watile, Rahul; Agasti, Soumitra; Naveen, Togati; Maiti, Debabrata

    2016-02-04

    Tremendous progress has been made towards ortho-selective C-H functionalization in the last three decades. However, the activation of distal C-H bonds and their functionalization has remained fairly underdeveloped. Herein, we report sequential meta-C-H functionalization by performing selective mono-olefination and bis-olefination with late stage modification of the C-Si as well as Si-O bonds. Temporary silyl connection was found to be advantageous due to its easy installation, easy removal and wide synthetic diversification.

  1. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  2. Ligand-enabled ortho-C-H olefination of phenylacetic amides with unactivated alkenes.

    Science.gov (United States)

    Lu, Ming-Zhu; Chen, Xing-Rong; Xu, Hui; Dai, Hui-Xiong; Yu, Jin-Quan

    2018-02-07

    Although chelation-assisted C-H olefination has been intensely investigated, Pd(ii)-catalyzed C-H olefination reactions are largely restricted to acrylates and styrenes. Here we report a quinoline-derived ligand that enables the Pd(ii)-catalyzed olefination of the C(sp 2 )-H bond with simple aliphatic alkenes using a weakly coordinating monodentate amide auxiliary. Oxygen is used as the terminal oxidant with catalytic copper as the co-oxidant. A variety of functional groups in the aliphatic alkenes are tolerated. Upon hydrogenation, the ortho -alkylated product can be accessed. The utility of this reaction is also demonstrated by the late-stage diversification of drug molecules.

  3. General allylic C-H alkylation with tertiary nucleophiles.

    Science.gov (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

    2014-04-16

    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  4. RIR MAPLE procedure for deposition of carbon rich Si/C/H films

    International Nuclear Information System (INIS)

    Dřínek, Vladislav; Strašák, Tomáš; Novotný, Filip; Fajgar, Radek; Bastl, Zdeněk

    2014-01-01

    We applied the resonant infrared matrix assisted pulsed laser evaporation (RIR MAPLE) technique to demonstrate a new approach to a controlled deposition of carbon rich amorphous Si/C/H film. In absence of radicals and accelerated species commonly generated in PECVD and sputtering setups, the RIR MAPLE method does not decompose precursor molecules. Moreover, unlike the standard MAPLE procedure, in which solvent molecules absorb laser energy from excimer or near infrared lasers, we applied the pulsed TEA CO 2 laser to excite the dendrimer precursor molecules in a frozen target. In this manner we achieved just cross-linking of the starting precursor on substrates and the deposition of carbon rich Si/C/H film. The film was analyzed by Fourier Transformed Infrared (FTIR), UV/VIS, Raman and X-ray Photoelectron (XPS) spectroscopy and Atomic Force Microscopy (AFM) technique. According to analyses the film retained the precursor elemental composition free of graphitic (sp 2 ) clusters. In course of reaction only the peripheral allyl groups containing C=C bonds were opened to achieve cross-linking. Whereas annealing to 300 °C was necessary for the elimination of =C–H 1 , 2 bonds in the films prepared at 200 °C, those bonds vanished completely for the films prepared at substrate temperature 255 °C. The film posseses a smooth surface with root mean square (RMS) parameter up to 10 nm within scanned distance 2.5 μm.

  5. RIR MAPLE procedure for deposition of carbon rich Si/C/H films

    Energy Technology Data Exchange (ETDEWEB)

    Dřínek, Vladislav, E-mail: drinek@icpf.cas.cz [Institute of Chemical Process Fundamentals of the ASCR, v. v. i., Rozvojova 135, 165 02 Prague 6 (Czech Republic); Strašák, Tomáš [Institute of Chemical Process Fundamentals of the ASCR, v. v. i., Rozvojova 135, 165 02 Prague 6 (Czech Republic); Novotný, Filip [Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University, 115 19 Prague (Czech Republic); Fajgar, Radek [Institute of Chemical Process Fundamentals of the ASCR, v. v. i., Rozvojova 135, 165 02 Prague 6 (Czech Republic); Bastl, Zdeněk [J. Heyrovsky Institute of Physical Chemistry of the ASCR, v. v. i., Dolejškova 2155/3, 182 23 Prague 8 (Czech Republic)

    2014-02-15

    We applied the resonant infrared matrix assisted pulsed laser evaporation (RIR MAPLE) technique to demonstrate a new approach to a controlled deposition of carbon rich amorphous Si/C/H film. In absence of radicals and accelerated species commonly generated in PECVD and sputtering setups, the RIR MAPLE method does not decompose precursor molecules. Moreover, unlike the standard MAPLE procedure, in which solvent molecules absorb laser energy from excimer or near infrared lasers, we applied the pulsed TEA CO{sub 2} laser to excite the dendrimer precursor molecules in a frozen target. In this manner we achieved just cross-linking of the starting precursor on substrates and the deposition of carbon rich Si/C/H film. The film was analyzed by Fourier Transformed Infrared (FTIR), UV/VIS, Raman and X-ray Photoelectron (XPS) spectroscopy and Atomic Force Microscopy (AFM) technique. According to analyses the film retained the precursor elemental composition free of graphitic (sp{sup 2}) clusters. In course of reaction only the peripheral allyl groups containing C=C bonds were opened to achieve cross-linking. Whereas annealing to 300 °C was necessary for the elimination of =C–H{sub 1}, {sub 2} bonds in the films prepared at 200 °C, those bonds vanished completely for the films prepared at substrate temperature 255 °C. The film posseses a smooth surface with root mean square (RMS) parameter up to 10 nm within scanned distance 2.5 μm.

  6. Measurement of the C / H ratio using neutrons; Mesure du rapport C / H au moyen des neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Martinelli, P [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires; Ricci, H [Universite de Lima (Peru)

    1960-07-01

    A probe made up of a Ra ({alpha}, n) Be neutron source and a proportional counter filled with boron trifluoride has been used to measure the C/H ratio in hydrocarbons. The intensity of the thermal neutron flux in the neighbourhood of the detector increases with the concentration of the hydrocarbon hydrogen surrounding it. By measuring the density it is possible to deduce the C/H ratio. It is thus possible to evaluate the C/H ratio with a precision equal to that given by the {beta}-ray transmission method. The errors arising from the chemical nature of the hydrocarbon can be reduced to a minimum. This method has the advantage of allowing the measurement of the C/H ratio of hydrocarbons contained in recipients or thick steel tubing by means an independent portable apparatus. (author) [French] Une sonde constituee d'une source de neutrons Ra ({alpha}, n) Be et d'un compteur proportionnel a remplissage de trifluorure de bore a ete utilisee pour mesurer le rapport C/H dans les hydrocarbures. Le flux des neutrons thermiques au voisinage du detecteur est d'autant plus intense que la concentration en hydrogene de l'hydrocarbure qui entoure la sonde est plus elevee. Une mesure de densite permet d'en deduire le rapport C/H. On peut ainsi evaluer le rapport C/H avec une precision aussi bonne que celle que l'on obtient par transmission de rayons {beta}. Les erreurs provenant de la nature chimique de l'hydrocarbure peuvent etre minimisees. Cette methode presente l'avantage de permettre la mesure du rapport C/H d'hydrocarbures contenus dans des recipients ou des canalisations epaisses en acier a l'aide d'un appareil exterieur transportable. (auteur)

  7. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation

    Science.gov (United States)

    Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

    2018-03-01

    The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

  8. Study of L-ascorbic acid (vitamin C)/H 2O mixture across glass transition

    Science.gov (United States)

    Migliardo, F.; Branca, C.; Faraone, A.; Magazù, S.; Migliardo, P.

    2001-07-01

    In this paper, we report quasi elastic neutron scattering (QENS) spectra of vitamin C aqueous solutions, obtained using MIBEMOL spectrometer (LLB). The main purpose of this work is to characterize the relaxational and vibrational properties of the Vitamin C/H 2O system below and above the glass transition temperature by analysing the low-frequency neutron scattering spectra. The determination of the relative weight of vibrational over relaxational contributions allows to get information on the fragility degree of this peculiar hydrogen-bond system.

  9. The dimers of glyoxal and acrolein with H 2O and HF: Negative intramolecular coupling and blue-shifted C-H stretch

    Science.gov (United States)

    Karpfen, Alfred; Kryachko, Eugene S.

    2010-04-01

    The structures and the vibrational spectra of the hydrogen-bonded complexes: glyoxal-H 2O, glyoxal-HF, acrolein-H 2O, and acrolein-HF, are investigated within the MP2/aug-cc-pVTZ computational approach. It is demonstrated that the calculated blue shifts of the C-H stretching frequencies in the glyoxal-H 2O complexes are only indirectly pertinent to hydrogen bonding to the C-H group. The comparison with the glyoxal-HF and the acrolein-HF complexes reveals that these blue shifts are a direct consequence of a negative intramolecular coupling between vicinal C dbnd O and C-H bonds in the aldehyde groups of isolated glyoxal and acrolein molecules. To support this interpretation, the halogen-bonded complexes glyoxal-BrF and acrolein-BrF are discussed.

  10. C-H functionalization directed by transformable nitrogen heterocycles: synthesis of ortho-oxygenated arylnaphthalenes from arylphthalazines.

    Science.gov (United States)

    Rastogi, Shiva K; Medellin, Derek C; Kornienko, Alexander

    2014-01-21

    Two protocols for oxygenation of aromatic C-H bonds ortho-positioned to the phthalazine ring were developed. The transannulation of the phthalazine ring to a naphthalene moiety by an Inverse Electron Demand Diels-Alder (IEDDA) reaction led to the synthesis of naphtho[2,1-c]chromenes, 1-(ortho-hydroxyaryl)naphthalenes and 6,7-dihydrobenzo[b]naphtho[1,2-d]oxepine. This new strategy based on the utilization of transformable nitrogen heterocycles in C-H functionalization chemistry can be potentially applicable to the synthesis of a broad range of biaryl compounds.

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

    Science.gov (United States)

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

    2015-06-01

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

  12. A Hydrazone-Based exo-Directing-Group Strategy for β C-H Oxidation of Aliphatic Amines.

    Science.gov (United States)

    Huang, Zhongxing; Wang, Chengpeng; Dong, Guangbin

    2016-04-18

    Described is a new hydrazone-based exo-directing group (DG) strategy developed for the functionalization of unactivated primary β C-H bonds of aliphatic amines. Conveniently synthesized from protected primary amines, the hydrazone DGs are shown to site-selectively promote the β-acetoxylation and tosyloxylation via five-membered exo-palladacycles. Amines with a wide scope of skeletons and functional groups are tolerated. Moreover, the hydrazone DG can be readily removed, and a one-pot C-H acetoxylation/DG removal protocol was also discovered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Atomic and electronic structures of a-SiC:H from tight-binding molecular dynamics

    CERN Document Server

    Ivashchenko, V I; Shevchenko, V I; Ivashchenko, L A; Rusakov, G V

    2003-01-01

    The atomic and electronic properties of amorphous unhydrogenated (a-SiC) and hydrogenated (a-SiC:H) silicon carbides are studied using an sp sup 3 s sup * tight-binding force model with molecular dynamics simulations. The parameters of a repulsive pairwise potential are determined from ab initio pseudopotential calculations. Both carbides are generated from dilute vapours condensed from high temperature, with post-annealing at low temperature for a-SiC:H. A plausible model for the inter-atomic correlations and electronic states in a-SiC:H is suggested. According to this model, the formation of the amorphous network is weakly sensitive to the presence of hydrogen. Hydrogen passivates effectively only the weak bonds of threefold-coordinated atoms. Chemical ordering is very much affected by the cooling rate and the structure of the high-temperature vapour. The as-computed characteristics are in rather good agreement with the results for a-SiC and a-Si:H from ab initio calculations.

  14. Properties of a-C:H:O plasma polymer films deposited from acetone vapors

    Energy Technology Data Exchange (ETDEWEB)

    Drabik, M., E-mail: martin.drabik@gmail.com [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland); Celma, C. [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland); Kousal, J.; Biederman, H. [Charles University in Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); Hegemann, D. [Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland)

    2014-12-31

    To gain insight into the deposition and stability of oxygen-containing plasma polymer films, the properties of amorphous oxygenated hydrocarbon (a-C:H:O) plasma polymer coatings deposited from acetone vapors under various experimental conditions are investigated. Apart from the discharge power, the influence of the reactive carbon dioxide (CO{sub 2}) gas on the structure of the resulting films is studied. It is found by characterization using X-ray Photoelectron Spectroscopy and Fourier-Transform Infrared Spectroscopy that the experimental conditions particularly influence the amount of oxygen in the deposited a-C:H:O plasma polymer films. The O/C elemental ratio increases with increasing amount of CO{sub 2} in the working gas mixture (up to 0.2 for 24 sccm of CO{sub 2} at 30 W) and decreases with increasing RF discharge power (down to 0.17 for 50 W). Furthermore, the nature of bonds between the oxygen and carbon atoms has been examined. Only low amounts of double and triple bonded carbon are observed. This has a particular influence on the aging of the plasma polymer films which is studied both in ambient air and in distilled water for up to 4 months. Overall, stable a-C:H:O plasma polymer films are deposited comprising low amounts (up to about 5%) of ester/carboxyl groups. - Highlights: • Hydrocarbon plasma polymer films with variable oxygen content can be prepared. • Stable oxygenated hydrocarbon plasma polymers contain max 5% of ester/carboxyl groups. • Acetone-derived plasma polymer films can be used as permanent hydrophilic surfaces.

  15. Measurement of 2J(H,C)- and 3J(H,C)-coupling constants by α/β selective HC(C)H-TOCSY

    International Nuclear Information System (INIS)

    Duchardt, Elke; Richter, Christian; Reif, Bernd; Glaser, Steffen J.; Engels, Joachim W.; Griesinger, Christian; Schwalbe, Harald

    2001-01-01

    A new heteronuclear NMR pulse sequence for the measurement of n J(C,H) coupling constants, the α/βselective HC(C)H-TOCSY, is described. It is shown that the S 3 E element (Meissner et al., 1997a,b) can be used to obtain spin state selective coherence transfer in molecules, in which adjacent CH moieties are labeled with 13 C. Application of the α/β selective HC(C)H-TOCSY to a 10nt RNA tetraloop 5'-CGCUUUUGCG-3', in which the four uridine residues are 13 C labeled in the sugar moiety, allowed measurement of two bond and three bond J(C,H) coupling constants, which provide additional restraints to characterize the sugar ring conformation of RNA in cases of conformational averaging

  16. Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

    Science.gov (United States)

    Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

    2017-12-18

    Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Carbon stars with alpha-C:H emission

    Science.gov (United States)

    Gerbault, Florence; Goebel, John H.

    1989-01-01

    Many carbon stars in the IRS low resolution spectra (LRS) catalog were found which display emission spectra that compare favorable with the absorption spectrum of alpha-C:H. These stars have largely been classified as 4X in the LRS which has led to their interpretation by others in terms of displaying a mixture of the UIRF's 8.6 micron band and SiC at 11.5 microns. It was also found that many of these stars have a spectral upturn at 20+ microns which resembles the MgS band seen in carbon stars and planetary nebulae. It was concluded that this group of carbon stars will evolve into planetary nebulae like NGC 7027 and IC 418. In the presence of hard ultraviolet radiation the UIRF's will light up and be displayed as narrow emission bands on top of the broad alpha-C:H emission bands.

  18. Oxyfunctionalization of the Remote C-H Bonds of Aliphatic Amines by Decatungstate Photocatalysis.

    Science.gov (United States)

    Schultz, Danielle M; Lévesque, François; DiRocco, Daniel A; Reibarkh, Mikhail; Ji, Yining; Joyce, Leo A; Dropinski, James F; Sheng, Huaming; Sherry, Benjamin D; Davies, Ian W

    2017-11-27

    Aliphatic amines, oxygenated at remote positions within the molecule, represent an important class of synthetic building blocks to which there are currently no direct means of access. Reported herein is an efficient and scalable solution that relies upon decatungstate photocatalysis under acidic conditions using either H 2 O 2 or O 2 as the terminal oxidant. By using these reaction conditions a series of simple and unbiased aliphatic amine starting materials can be oxidized to value-added ketone products. Lastly, NMR spectroscopy using in situ LED-irradiated samples was utilized to monitor the kinetics of the reaction, thus enabling direct translation of the reaction into flow. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights

    KAUST Repository

    Ajitha, Manjaly John

    2016-03-29

    The possibility of direct introduction of a new functionality through C–H bond activation is an attractive strategy in covalent synthesis. Here, we investigated the mechanism of Rh-catalysed C-H amination of the hetero-aryl substrate (2-phenylpyridine) using phenyl azide as nitrogen source by density functional theory (DFT). For the deprotocyclometallation and protodecyclometallation processes of the title reaction, we propose a stepwise base-assisted mechanism (pathway I) instead of previously reported concerted mechanism (pathway II). In the new mechanism proposed here, 2-phenylpyridine acts as a base in the initial deprotonation step (C-H bond cleavage) and transports the proton towards the final protonation step. In fact, the N-H bond of the strong conjugate acid (formed during initial C-H bond cleavage) considered in pathway I (via TS4) is more acidic than the C-H bond of the neutral substrate considered in pathway II (via TS5). The higher activation barrier of TS5 mainly originates from the ring strain of the four membered cyclic transition state. The vital role of base, as disclosed here, can potentially have broader mechanistic implications for the development of reaction conditions of transition metal catalysed reactions.

  20. Microstructure of a-C:H films prepared on a microtrench and analysis of ions and radicals behavior

    Science.gov (United States)

    Hirata, Yuki; Choi, Junho

    2015-08-01

    Amorphous carbon films (a-C:H) were prepared on a microtrench (4-μm pitch and 4-μm depth), and the uniformity of film thickness and microstructure of the films on the top, sidewall, and bottom surfaces of the microtrench were evaluated by scanning electron microscopy and Raman spectroscopy. The a-C:H films were prepared by bipolar-type plasma based ion implantation and deposition (bipolar PBII&D), and the negative pulse voltage, which is the main parameter dominating the film structure, was changed from -1.0 to -15 kV. Moreover, the behavior of ions and radicals was analyzed simultaneously by combining the calculation methods of Particle-In-Cell/Monte Carlo Collision (PIC-MCC) and Direct Simulation Monte Carlo (DSMC) to investigate the coating mechanism for the microtrench. The results reveal that the thickness uniformity of a-C:H films improves with decreasing negative pulse voltage due to the decreasing inertia of incoming ions from the trench mouth, although the film thickness on the sidewall tends to be much smaller than that on the top and bottom surfaces of the trench. The normalized flux and the film thickness show similar behavior, i.e., the normalized flux or thickness at the bottom surface increases at low negative pulse voltages and then saturates at a certain value, whereas at the sidewall it monotonically decreases with increasing negative voltage. The microstructure of a-C:H films on the sidewall surface is very different from that on the top and bottom surfaces. The film structure at a low negative pulse voltage shifts to more of a polymer-like carbon (PLC) structure due to the lower incident energy of ions. Although the radical flux on the sidewall increases slightly, the overall film structure is not significantly changed because this film formation at a low negative voltage is originally dominated by radicals. On the other hand, the flux of radicals is dominant on the sidewall in the case of high negative pulse voltage, resulting in a deviation

  1. Microstructure of a-C:H films prepared on a microtrench and analysis of ions and radicals behavior

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, Yuki; Choi, Junho, E-mail: choi@mech.t.u-tokyo.ac.jp [Department of Mechanical Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)

    2015-08-28

    Amorphous carbon films (a-C:H) were prepared on a microtrench (4-μm pitch and 4-μm depth), and the uniformity of film thickness and microstructure of the films on the top, sidewall, and bottom surfaces of the microtrench were evaluated by scanning electron microscopy and Raman spectroscopy. The a-C:H films were prepared by bipolar-type plasma based ion implantation and deposition (bipolar PBII&D), and the negative pulse voltage, which is the main parameter dominating the film structure, was changed from −1.0 to −15 kV. Moreover, the behavior of ions and radicals was analyzed simultaneously by combining the calculation methods of Particle-In-Cell/Monte Carlo Collision (PIC-MCC) and Direct Simulation Monte Carlo (DSMC) to investigate the coating mechanism for the microtrench. The results reveal that the thickness uniformity of a-C:H films improves with decreasing negative pulse voltage due to the decreasing inertia of incoming ions from the trench mouth, although the film thickness on the sidewall tends to be much smaller than that on the top and bottom surfaces of the trench. The normalized flux and the film thickness show similar behavior, i.e., the normalized flux or thickness at the bottom surface increases at low negative pulse voltages and then saturates at a certain value, whereas at the sidewall it monotonically decreases with increasing negative voltage. The microstructure of a-C:H films on the sidewall surface is very different from that on the top and bottom surfaces. The film structure at a low negative pulse voltage shifts to more of a polymer-like carbon (PLC) structure due to the lower incident energy of ions. Although the radical flux on the sidewall increases slightly, the overall film structure is not significantly changed because this film formation at a low negative voltage is originally dominated by radicals. On the other hand, the flux of radicals is dominant on the sidewall in the case of high negative pulse voltage, resulting in a

  2. Inserção C-H de carbenóides de ródio em água e reutilização do catalisador Rhodium (II carbene C-H insertion in water and catalyst reuse

    Directory of Open Access Journals (Sweden)

    Nuno R. Candeias

    2007-01-01

    Full Text Available A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonylacetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh2(OAc4. The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization.

  3. C-H Activation and Alkyne Annulation via Automatic or Intrinsic Directing Groups: Towards High Step Economy.

    Science.gov (United States)

    Zheng, Liyao; Hua, Ruimao

    2018-06-01

    Direct transformation of carbon-hydrogen bond (C-H) has emerged to be a trend for construction of molecules from building blocks with no or less prefunctionalization, leading high atom and step economy. Directing group (DG) strategy is widely used to achieve higher reactivity and selectivity, but additional steps are usually needed for installation and/or cleavage of DGs, limiting step economy of the overall transformation. To meet this challenge, we proposed a concept of automatic DG (DG auto ), which is auto-installed and/or auto-cleavable. Multifunctional oxime and hydrazone DG auto were designed for C-H activation and alkyne annulation to furnish diverse nitrogen-containing heterocycles. Imidazole was employed as an intrinsic DG (DG in ) to synthesize ring-fused and π-extended functional molecules. The alkyne group in the substrates can also be served as DG in for ortho-C-H activation to afford carbocycles. In this account, we intend to give a review of our progress in this area and brief introduction of other related advances on C-H functionalization using DG auto or DG in strategies. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Influence of nitrogen on the tribological properties of a-C:H layers on the polycarbonate substrates

    Directory of Open Access Journals (Sweden)

    Rafal M. Nowak

    2008-12-01

    Full Text Available Polycarbonate (PC possesses many commercial applications. However, PC is still limited to non-abrasive and chemical-free environments due to its low hardness, low scratching resistance and high susceptibility to chemical attacks. To overcome this limitation, PC can be coated by hydrogenated amorphous carbon layers. The a-C:H layers have very attractive properties such as high hardness, infrared transparency, chemical inertness, low friction coefficients, and biocompatibility. Addition of nitrogen in the structure allows lowering internal stress and improve tribological properties of a-C:H layers. In this work, a-C:N:H layers were deposited from mixture CH4/N2 gases by RF PECVD method. Effects of the nitrogen incorporation on structure and tribological properties of deposited layers were investigated. The structure of layers were characterized by Fourier Transform Infrared spectroscopy (FTIR and X-ray photoelectron spectroscopy (XPS. The friction coefficient, wear resistance of a-C:H:N layers were estimated by tribometer in ball-on-disc configuration. The IR spectra of the obtained layers have demonstrated a presence of nitrogen bonded both to carbon and to hydrogen. A formation of the following bonds has been confirmed: -C≡N, -NH2, -C−NH2, >C=NH. They are all typical for a-C:N:H layers. The tribological tests have shown that the layers reduce the friction coefficient of the polycarbonate (up to 50 % and considerably improve wear resistance.

  5. A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights

    KAUST Repository

    Ajitha, Manjaly John; Huang, Kuo-Wei; Kwak, Jaesung; Kim, Hyun Jin; Chang, Sukbok; Jung, Yousung

    2016-01-01

    The possibility of direct introduction of a new functionality through C–H bond activation is an attractive strategy in covalent synthesis. Here, we investigated the mechanism of Rh-catalysed C-H amination of the hetero-aryl substrate (2

  6. Alcohols as alkylating agents in heteroarene C?H functionalization

    OpenAIRE

    Jin, Jian; MacMillan, David W. C.

    2015-01-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage 1 . One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ?spin-center shift? (SCS) 2 , during which an alcohol C?O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilize...

  7. The HCClF_2-HCCH Complex: Microwave Spectrum, Structure and C-H\\cdotsπ Interactions

    Science.gov (United States)

    Peebles, Rebecca A.; Sexton, John M.; Elliott, Ashley A.; Steber, Amanda L.; Peebles, Sean A.; Neill, Justin L.; Muckle, Matt T.; Pate, Brooks H.

    2010-06-01

    The HCF_3-HCCH complex was recently found to have a weak C-H\\cdotsπ interaction between the fluoroform and acetylene, as well as having a secondary interaction between the fluorine atoms and one of the acetylene hydrogen atoms; however, extensive splittings due to large amplitude motions within the complex have complicated our efforts at making a full assignment of the HCF_3-HCCH spectrum. In an attempt to remove some of the ambiguity in the HCF_3-HCCH study, we have substituted a chlorine atom for one fluorine atom and undertaken an investigation of the HCClF_2-HCCH complex. This eliminates the possibility of internal rotation of the methane subunit, while still maintaining a C-H\\cdotsπ interaction. Using the chirped-pulse Fourier-transform microwave (CP-FTMW) spectrometer at the University of Virginia and the Balle-Flygare FTMW spectrometer at Eastern Illinois University, the spectra of four isotopologues of HCClF_2-HCCH have been assigned, with no indication of internal motions within the complex. The structure has been determined from the experimental moments of inertia, confirming that this dimer has the expected weak C-H\\cdotsπ interaction. In addition, the off-diagonal χab quadrupole coupling constant has been used to determine the angle between the C-Cl bond and the a-axis of the complex. This, and Kraitchman coordinates for the chlorine atom, help confirm the structural details from the inertial fit. The structural results will be compared with other complexes showing C-H\\cdotsπ and C-H\\cdotsO interactions. S. A. Peebles, M. M. Serafin, R. A. Peebles, 61st International Symposium on Molecular Spectroscopy, Talk MH13, June 19, 2006.

  8. 1,4-Iron Migration for Expedient Allene Annulations through Iron-Catalyzed C-H/N-H/C-O/C-H Functionalizations.

    Science.gov (United States)

    Mo, Jiayu; Müller, Thomas; Oliveira, João C A; Ackermann, Lutz

    2018-06-25

    C-H activation bears great potential for enabling sustainable molecular syntheses in a step- and atom-economical manner, with major advances having been realized with precious 4d and 5d transition metals. In contrast, we employed earth abundant, nontoxic iron catalysts for versatile allene annulations through a unique C-H/N-H/C-O/C-H functionalization sequence. The powerful iron catalysis occurred under external-oxidant-free conditions even at room temperature, while detailed mechanistic studies revealed an unprecedented 1,4-iron migration regime for facile C-H activations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

    Science.gov (United States)

    Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

    2014-12-01

    Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

  10. A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.

    Science.gov (United States)

    Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M

    2016-06-17

    The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

  11. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

    Science.gov (United States)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen

    2015-05-01

    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader's quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN (1Σ) and hydrideisocyanidezinc HZnNC (1Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]+ composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn+ (2Σ) and HCNZn+ (2Σ).

  12. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

    International Nuclear Information System (INIS)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen

    2015-01-01

    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader’s quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ( 1 Σ) and hydrideisocyanidezinc HZnNC ( 1 Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn] + composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn + ( 2 Σ) and HCNZn + ( 2 Σ)

  13. Incorporated W Roles on Microstructure and Properties of W-C:H Films by a Hybrid Linear Ion Beam Systems

    Directory of Open Access Journals (Sweden)

    Peng Guo

    2013-01-01

    Full Text Available W-incorporated diamond-like carbon (W-C:H films were fabricated by a hybrid beams system consisting of a DC magnetron sputtering and a linear ion source. The W concentration (1.08~31.74 at.% in the film was controlled by varying the sputtering current. The cross-sectional topography, composition, and microstructure of the W-C:H films were investigated by SEM, XPS, TEM, and Raman spectroscopy. The mechanical and tribological properties of the films as a function of W concentration were evaluated by a stress-tester, nanoindentation, and ball-on-disk tribometer, respectively. The results showed that films mainly exhibited the feature of amorphous carbon when W concentration of the films was less than 4.38 at.%, where the incorporated W atoms would be bonded with C atoms and resulted in the formation of WC1-x nanoparticles. The W-C:H film with 4.38 at.% W concentration showed a minimum value of residual compressive stress, a higher hardness, and better tribological properties. Beyond this W concentration range, both the residual stress and mechanical properties were deteriorated due to the growth of tungsten carbide nanoparticles in the carbon matrix.

  14. Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen, E-mail: cbb@qf.uva.es [Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid (Spain)

    2015-05-14

    The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader’s quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ({sup 1}Σ) and hydrideisocyanidezinc HZnNC ({sup 1}Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]{sup +} composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn{sup +} ({sup 2}Σ) and HCNZn{sup +} ({sup 2}Σ)

  15. Aging of oxygen and hydrogen plasma discharge treated a-C:H and ta-C coatings

    Energy Technology Data Exchange (ETDEWEB)

    Bachmann, Svenja [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Schulze, Marcus [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Morasch, Jan [Institute of Materials Science, Technische Universität Darmstadt, Surface Science Division, Jovanka-Bonschits-Straße 2, 64287 Darmstadt (Germany); Hesse, Sabine [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Hussein, Laith [Eduard-Zintl-Institut, Department of Chemistry, Technische Universität Darmstadt, Alarich-Weiss-Str. 12, 64287, Darmstadt (Germany); Krell, Lisa; Schnagl, Johann [BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Stark, Robert W. [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); and others

    2016-05-15

    Highlights: • The water CA of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C changes from hydrophillic to hydrophobic on aging. • XPS study indicates that the decrease in surface energy of plasma treated a-C:H and ta-C could be due to adsorption of organic component from air. • The COFLFM of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C decreased upon aging. • The COF of glycerol lubricated ta-C showed no sign of change upon aging. - Abstract: Surface modification with gas plasma is an efficient and easy way to improve the surface energy and the tribological behavior of diamond-like carbon (DLC) coatings, e.g., in biomedical implants or as protective coatings. However, the long-term performance of the plasma treated DLC coatings is not fully clear. We thus studied the long-term stability of two kinds of DLC coatings, namely (a) hydrogenated amorphous carbon (a-C:H) and (b) tetrahedral amorphous carbon (ta-C) treated at different radio frequency (RF) power and time of oxygen (O{sub 2}) and hydrogen (H{sub 2}) plasma. Their surface properties, e.g. surface wettability, structure and tribological behavior, were studied at regular intervals for a period of two months using contact angle goniometer, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), lateral force microscopy (LFM) and ball on disc apparatus. The surface energy of both the coatings decreased upon aging. The higher the RF power and time of treatment, the higher was the hydrophobicity upon aging. XPS analysis showed that the increase in hydrophobicity could be due to adsorption of unavoidable volatile organic components in the atmosphere. The H{sub 2} plasma treated ta-C was capable of rearranging its structural bonds upon aging. The nano-friction measurements by LFM showed that the coefficient of friction of plasma treated a-C:H and ta-C decreased upon aging. The results indicate that the surface properties of plasma treated a‐C:H and ta‐C are not stable on long-term and are

  16. Study of the hydrogen behavior in amorphous hydrogenated materials of type a - C:H and a - SiC:H facing fusion reactor plasma

    International Nuclear Information System (INIS)

    Barbier, G.

    1997-01-01

    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author)

  17. Hydrogen behaviour study in plasma facing a-C:H and a-SiC:H hydrogenated amorphous materials for fusion reactors

    International Nuclear Information System (INIS)

    Barbier, Gauzelin

    1997-01-01

    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. Firstly, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce this interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a-SiC:H substrate can be benefit in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a -SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a-C:H and a-SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modeling of hydrogen diffusion under irradiation has been also proposed. (author)

  18. Alcohols as alkylating agents in heteroarene C-H functionalization

    Science.gov (United States)

    Jin, Jian; MacMillan, David W. C.

    2015-09-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  19. Alcohols as alkylating agents in heteroarene C-H functionalization.

    Science.gov (United States)

    Jin, Jian; MacMillan, David W C

    2015-09-03

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of 'spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  20. Ag1 Pd1 Nanoparticles-Reduced Graphene Oxide as a Highly Efficient and Recyclable Catalyst for Direct Aryl C-H Olefination.

    Science.gov (United States)

    Hu, Qiyan; Liu, Xiaowang; Wang, Guoliang; Wang, Feifan; Li, Qian; Zhang, Wu

    2017-12-14

    The efficient and selective palladium-catalyzed activation of C-H bonds is of great importance for the construction of diverse bioactive molecules. Despite significant progress, the inability to recycle palladium catalysts and the need for additives impedes the practical applications of these reactions. Ag 1 Pd 1 nanoparticles-reduced graphene oxide (Ag 1 Pd 1 -rGO) was used as highly efficient and recyclable catalyst for the chelation-assisted ortho C-H bond olefination of amides with acrylates in good yields with a broad substrate scope. The catalyst can be recovered and reused at least 5 times without losing activity. A synergistic effect between the Ag and Pd atoms on the catalytic activity was found, and a plausible mechanism for the AgPd-rGO catalyzed C-H olefination is proposed. These findings suggest that the search for such Pd-based bimetallic alloy nanoparticles is a new method towards the development of superior recyclable catalysts for direct aryl C-H functionalization under mild conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Recent advances in the ruthenium(ii)-catalyzed chelation-assisted C-H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2017-08-08

    The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

  2. The I{sub c}(H)-T{sub c}(H) phase boundary of superconducting Nb thin films with periodic and quasiperiodic antidot arrays

    Energy Technology Data Exchange (ETDEWEB)

    Bothner, D.; Kemmler, M.; Cozma, R.; Kleiner, R.; Koelle, D. [Physikalisches Institut and Center for Collective Quantum Phenomena, Universitaet Tuebingen (Germany); Misko, V.; Peeters, F. [Departement Fysica, Universiteit Antwerpen (Belgium); Nori, F. [Advanced Science Institute, RIKEN (Japan)

    2011-07-01

    The magnetic field dependent critical current I{sub c}(H) of superconducting thin films with artificial defects strongly depends on the symmetry of the defect arrangement. Likewise the critical temperature T{sub c}(H) of superconducting wire networks is heavily influenced by the symmetry of the system. Here we present experimental data on the I{sub c}(H)-T{sub c}(H) phase boundary of Nb thin films with artificial defect lattices of different symmetries. For this purpose we fabricated 60 nm thick Nb films with antidots in periodic (triangular) and five different quasiperiodic arrangements. The parameters of the antidot arrays were varied to investigate the influence of antidot diameter and array density. Experiments were performed with high temperature stability ({delta}T<1 mK) at 0.5{<=}T/T{sub c}{<=}1. From the I-V-characteristics at variable H and T we extract I{sub c}(H) and T{sub c}(H) for different voltage and resistance criteria. The experimental data for the critical current density are compared with results from numerical molecular dynamics simulations.

  3. Carlos Romero

    Directory of Open Access Journals (Sweden)

    2008-05-01

    Full Text Available Entrevista (en español Presentación Carlos Romero, politólogo, es profesor-investigador en el Instituto de Estudios Políticos de la Facultad de Ciencias Jurídicas y Políticas de la Universidad Central de Venezuela, en donde se ha desempeñado como coordinador del Doctorado, subdirector y director del Centro de Estudios de Postgrado. Cuenta con ocho libros publicados sobre temas de análisis político y relaciones internacionales, siendo uno de los últimos Jugando con el globo. La política exter...

  4. Ruthenium(II)-Catalyzed C-H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate-Controlled Synthesis of Indoles and 3H-Indoles.

    Science.gov (United States)

    Li, Yunyun; Qi, Zisong; Wang, He; Yang, Xifa; Li, Xingwei

    2016-09-19

    Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor-acceptor diazo compounds were developed that afforded NH indoles and 3H-indoles under ruthenium catalysis. The coupling of α-diazoketoesters afforded NH indoles by cleavage of the C(N2 )-C(acyl) bond whereas α-diazomalonates gave 3H-indoles by C-N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium-catalyzed C-H activation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Catalyst- and Reagent-free Electrochemical Azole C-H Amination.

    Science.gov (United States)

    Qiu, Youai; Struwe, Julia; Meyer, Tjark H; Oliveira, Joao Carlos Agostinho Carlos Agostinho; Ackermann, Lutz

    2018-06-14

    Catalyst-, and chemical oxidant-free electrochemical azole C-H aminations were accomplished via cross-dehydrogenative C-H/N-H functionalization. The catalyst-free electrochemical C-H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp3)-H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C-H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effect of deposition temperature and thermal annealing on the dry etch rate of a-C: H films for the dry etch hard process of semiconductor devices

    International Nuclear Information System (INIS)

    Lee, Seung Moo; Won, Jaihyung; Yim, Soyoung; Park, Se Jun; Choi, Jongsik; Kim, Jeongtae; Lee, Hyeondeok; Byun, Dongjin

    2012-01-01

    The effect of deposition and thermal annealing temperatures on the dry etch rate of a-C:H films was investigated to increase our fundamental understanding of the relationship between thermal annealing and dry etch rate and to obtain a low dry etch rate hard mask. The hydrocarbon contents and hydrogen concentration were decreased with increasing deposition and annealing temperatures. The I(D)/I(G) intensity ratio and extinction coefficient of the a-C:H films were increased with increasing deposition and annealing temperatures because of the increase of sp 2 bonds in the a-C:H films. There was no relationship between the density of the unpaired electrons and the deposition temperature, or between the density of the unpaired electrons and the annealing temperature. However, the thermally annealed a-C:H films had fewer unpaired electrons compared with the as-deposited ones. Transmission electron microscopy analysis showed the absence of any crystallographic change after thermal annealing. The density of the as-deposited films was increased with increasing deposition temperature. The density of the 600 °C annealed a-C:H films deposited under 450 °C was decreased but at 550 °C was increased, and the density of all 800 °C annealed films was increased. The dry etch rate of the as-deposited a-C:H films was negatively correlated with the deposition temperature. The dry etch rate of the 600 °C annealed a-C:H films deposited at 350 °C and 450 °C was faster than that of the as-deposited film and that of the 800 °C annealed a-C:H films deposited at 350 °C and 450 °C was 17% faster than that of the as-deposited film. However, the dry etch rate of the 550 °C deposited a-C:H film was decreased after annealing at 600 °C and 800 °C. The dry etch rate of the as-deposited films was decreased with increasing density but that of the annealed a-C:H films was not. These results indicated that the dry etch rate of a-C:H films for dry etch hard masks can be further decreased by

  7. 激光熔覆TiC-H13涂层的微结构及耐腐蚀性能的研究%Study on Microstructure and Electrochemical Corrosion Resistance of Laser Cladding TiC-H13 Steel Composite Coating

    Institute of Scientific and Technical Information of China (English)

    杨倩; 黄宛真; 孔凡志

    2016-01-01

    TiC-H 13 cladding layer was produced by laser cladding on H 13 steel substrate.The effects of TiC on microstructure and electrochemical corrosion behavior of TiC-H13 layer were studied by SEM,EDS,TEM and anodic polarization curve.The results show that good metallurgical bonding is formed between the TiC-H 13 cladding layer and H 13 steel substrate.The new phase of TiC is formed in the laser cladding layer.Compared with H13 steel,the TiC-H13 cladding layer demonstrates much higher corrosion potential and the lower corrosion current,which exhibites significantly higher corrosion resistant.%以H13钢为基体,通过激光熔覆TiC-H13混合粉末获得熔覆层,考察TiC的加入对TiC-H13熔覆层的微观结构以及耐腐蚀性能的影响.采用SEM、EDS和TEM对熔覆层内的微观组成和物相进行表征,利用电化学阳极极化曲线研究熔覆层的耐腐蚀性能.结果表明:TiC-H13粉末和H13钢基体可以形成良好的熔覆层,熔覆层与基体紧密结合,熔覆层中形成新物相TiC.与H13钢相比,TiC-H 13熔覆层的腐蚀电位明显升高,腐蚀电流明显降低,耐腐蚀性能得到显著提高.

  8. Thin films of hydrogenated amorphous carbon (a-C:H) obtained through chemical vapor deposition assisted by plasma; Peliculas delgadas de carbono amorfo hidrogenado (a-C:H) obtenidas mediante deposito quimico de vapores asistido por plasma

    Energy Technology Data Exchange (ETDEWEB)

    Mejia H, J.A.; Camps C, E.E.; Escobar A, L.; Romero H, S.; Chirino O, S. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Muhl S, S. [IIM-UNAM, 04510 Mexico D.F. (Mexico)

    2004-07-01

    Films of hydrogenated amorphous carbon (a-C:H) were deposited using one source of microwave plasma with magnetic field (type ECR), using mixtures of H{sub 2}/CH{sub 4} in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10{sup -4} to 6x10{sup -4} Torr and an incident power of the discharge of microwaves with a constant value of 400 W. It was analyzed the influence among the properties of the films, as the deposit rate, the composition and the bonding types, and the deposit conditions, such as the flow rates of the precursory gases and the polarization voltage of the sample holders. (Author)

  9. Breakdown of the Coulomb friction law in TiC/a-C : H nanocomposite coatings

    NARCIS (Netherlands)

    Pei, Y.T.; Huizenga, P.; Galvan, D.; Hosson, J.Th.M. De

    2006-01-01

    Advanced TiC/a-C:H nanocomposite coatings have been produced via reactive deposition in a closed-field unbalanced magnetron sputtering system (Hauzer HTC-1000 or HTC 1200). In this paper, we report on the tribological behavior of TiC/a-C:H nanocomposite coatings in which ultralow friction is

  10. Advanced TiC/a-C : H nanocomposite coatings deposited by magnetron sputtering

    NARCIS (Netherlands)

    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De; Strondl, C.

    2006-01-01

    TiC/a-C:H nanocomposite coatings have been deposited by magnetron Sputtering. They consist of 2-5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a Columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing

  11. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids

    Science.gov (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan

    2009-01-01

    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  12. S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes

    NARCIS (Netherlands)

    Naksomboon, K.; Valderas, C.; Gomez-Martinez, M.; Alvarez-Casao, Y.; Fernández Ibáñez, M.A.

    Pd(II)-catalyzed C-H functionalization of non directed arenes has been realized using an inexpensive and easily accessible type of bidentate S,O-ligand. The catalytic system shows high efficiency in the C-H olefination reaction of electron-rich and electron-poor arenes. This methodology is

  13. Aging of oxygen and hydrogen plasma discharge treated a-C:H and ta-C coatings

    Science.gov (United States)

    Bachmann, Svenja; Schulze, Marcus; Morasch, Jan; Hesse, Sabine; Hussein, Laith; Krell, Lisa; Schnagl, Johann; Stark, Robert W.; Narayan, Suman

    2016-05-01

    Surface modification with gas plasma is an efficient and easy way to improve the surface energy and the tribological behavior of diamond-like carbon (DLC) coatings, e.g., in biomedical implants or as protective coatings. However, the long-term performance of the plasma treated DLC coatings is not fully clear. We thus studied the long-term stability of two kinds of DLC coatings, namely (a) hydrogenated amorphous carbon (a-C:H) and (b) tetrahedral amorphous carbon (ta-C) treated at different radio frequency (RF) power and time of oxygen (O2) and hydrogen (H2) plasma. Their surface properties, e.g. surface wettability, structure and tribological behavior, were studied at regular intervals for a period of two months using contact angle goniometer, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), lateral force microscopy (LFM) and ball on disc apparatus. The surface energy of both the coatings decreased upon aging. The higher the RF power and time of treatment, the higher was the hydrophobicity upon aging. XPS analysis showed that the increase in hydrophobicity could be due to adsorption of unavoidable volatile organic components in the atmosphere. The H2 plasma treated ta-C was capable of rearranging its structural bonds upon aging. The nano-friction measurements by LFM showed that the coefficient of friction of plasma treated a-C:H and ta-C decreased upon aging. The results indicate that the surface properties of plasma treated a-C:H and ta-C are not stable on long-term and are influenced by the environmental conditions.

  14. XPS study of the ultrathin a-C:H films deposited onto ion beam nitrided AISI 316 steel

    International Nuclear Information System (INIS)

    Meskinis, S.; Andrulevicius, M.; Kopustinskas, V.; Tamulevicius, S.

    2005-01-01

    Effects of the steel surface treatment by nitrogen ion beam and subsequent deposition of the diamond-like carbon (hydrogenated amorphous carbon (a-C:H) and nitrogen doped hydrogenated amorphous carbon (a-CN x :H)) films were investigated by means of the X-ray photoelectron spectroscopy (XPS). Experimental results show that nitrogen ion beam treatment of the AISI 316 steel surface even at room temperature results in the formation of the Cr and Fe nitrides. Replacement of the respective metal oxides by the nitrides takes place. Formation of the C-N bonds was observed for both ultrathin a-C:H and ultrathin a-CN x :H layers deposited onto the nitrided steel. Some Fe and/or Cr nitrides still were presented at the interface after the film deposition, too. Increased adhesion between the steel substrate and hydrogenated amorphous carbon layer after the ion beam nitridation was explained by three main factors. The first two is steel surface deoxidisation/passivation by nitrogen as a result of the ion beam treatment. The third one is carbon nitride formation at the nitrided steel-hydrogenated amorphous carbon (or a-CN x :H) film interface

  15. Thin films of hydrogenated amorphous carbon (a-C:H) obtained through chemical vapor deposition assisted by plasma

    International Nuclear Information System (INIS)

    Mejia H, J.A.; Camps C, E.E.; Escobar A, L.; Romero H, S.; Chirino O, S.; Muhl S, S.

    2004-01-01

    Films of hydrogenated amorphous carbon (a-C:H) were deposited using one source of microwave plasma with magnetic field (type ECR), using mixtures of H 2 /CH 4 in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10 -4 to 6x10 -4 Torr and an incident power of the discharge of microwaves with a constant value of 400 W. It was analyzed the influence among the properties of the films, as the deposit rate, the composition and the bonding types, and the deposit conditions, such as the flow rates of the precursory gases and the polarization voltage of the sample holders. (Author)

  16. Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcohols

    KAUST Repository

    Poater, Albert

    2016-09-11

    Density functional theory calculations have been used to investigate the reaction mechanism for [(C6H6)(PCy3)(CO) RuH](+) (1; Cy, cyclohexyl) mediated alkylation of indene substrate using ethanol as solvent. According to Yi et al. [ Science 2011, 333, 1613] the plausible reaction mechanism involves a cationic Rualkenyl species, which is initially formed from 1 with two equivalents of the olefin substrate via the vinylic C-H activation and an alkane elimination step. Once the active catalytic species is achieved the oxidative addition step is faced. The latter step together with the next C-C bond formation might display the upper barrier of the catalytic cycle. Having these experimental insights at hand, we investigated in detail the whole reaction pathway using several computational DFT approaches including alternative pathways, higher in energy.

  17. Study of the hydrogen behavior in amorphous hydrogenated materials of type a - C:H and a - SiC:H facing fusion reactor plasma; Etude du comportament de l`hydrogene dans des materiaux amorphes hydrogenes de type a - C:H et a - SiC:H devant faire face au plasma des reacteurs a fusion

    Energy Technology Data Exchange (ETDEWEB)

    Barbier, G. [Lyon-1 Univ., 69 - Villeurbanne (France). Inst. de Physique Nucleaire

    1997-04-10

    Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author) 176 refs.

  18. Identification of nanoscale structure and morphology reconstruction in oxidized a-SiC:H thin films

    Energy Technology Data Exchange (ETDEWEB)

    Vasin, A.V.; Rusavsky, A.V.; Nazarov, A.N.; Lysenko, V.S.; Lytvyn, P.M.; Strelchuk, V.V. [Lashkaryov Institute of Semiconductor Physics, 41 Nauki Pr., Kiev 03028 (Ukraine); Kholostov, K.I.; Bondarenko, V.P. [Belarusian State University of Informatics and Radioelectronics, 6P. Brovki Str., Minsk 220013 (Belarus); Starik, S.P. [Bakul Institute of Superhard Materials, 2 Avtzavodskaya Str., Kiev 04074 (Ukraine)

    2012-11-01

    Highlights: Black-Right-Pointing-Pointer Increase of magnetron discharge power results in densification of a-SiC:H thin films. Black-Right-Pointing-Pointer The denser a-SiC:H material the better resistance to oxidation by oxygen. Black-Right-Pointing-Pointer Oxidation of soft a-SiC:H films can result in increase of electric conductivity. Black-Right-Pointing-Pointer Formation of graphitic clusters was found in a-SiC:H after annealing in oxygen. - Abstract: Oxidation behavior of a-SiC:H layers deposited by radio-frequency magnetron sputtering technique was examined by Kelvin probe force microscopy (KPFM) in combination with scanning electron microscopy, Fourier-transform infra-red spectroscopy and submicron selected area Raman scattering spectroscopy. Partially oxidized a-SiC:H samples (oxidation at 600 Degree-Sign C in oxygen) were examined to clarify mechanism of the oxidation process. Nanoscale and microscale morphological defects (pits) with dimension of about 50 nm and several microns respectively have appeared after thermal treatment. KPFM measurements exhibited the surface potential of the material in micro pits is significantly smaller in comparison with surrounding material. Submicron RS measurements indicates formation of graphite-like nano-inclusions in the pit defects. We conclude that initial stage of oxidation process in a-SiC:H films takes place not homogeneously throughout the layer but it is initiated in local nanoscale regions followed by spreading over all layer.

  19. Use of the Wilkinson catalyst for the ortho-C-H heteroarylation of aromatic amines: facile access to highly extended π-conjugated heteroacenes for organic semiconductors.

    Science.gov (United States)

    Huang, Yumin; Wu, Di; Huang, Jingsheng; Guo, Qiang; Li, Juan; You, Jingsong

    2014-11-03

    An unprecedented catalytic system composed of the Wilkinson catalyst [Rh(PPh3)3Cl] and CF3COOH enabled the highly regioselective cross-coupling of aromatic amines with a variety of heteroarenes through dual C-H bond cleavage. This protocol provided a facile and rapid route from readily available substrates to (2-aminophenyl)heteroaryl compounds, which may be conveniently transformed into highly extended π-conjugated heteroacenes. The experimental studies and calculations showed that thianaphtheno[3,2-b]indoles have large HOMO-LUMO energy gaps and low-lying HOMO levels, and could therefore potentially be high-performance organic semiconductors. Herein we report the first use of a rhodium(I) catalyst for oxidative C-H/C-H coupling reactions. The current innovative catalyst system is much less expensive than [RhCp*Cl2]2/AgSbF6 and could open the door for the application of this approach to other types of C-H activation processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  1. Synergistic Manganese(I) C-H Activation Catalysis in Continuous Flow: Chemoselective Hydroarylation.

    Science.gov (United States)

    Wang, Hui; Pesciaioli, Fabio; Oliveira, João C A; Warratz, Svenja; Ackermann, Lutz

    2017-11-20

    Chemoselective hydroarylations were accomplished by a novel synergistic Brønsted acid/manganese(I)-catalyzed C-H activation manifold. Thus, alkynes bearing O-leaving groups could, for the first time, be employed for C-H alkenylations without concurrent β-O elimination, thereby setting the stage for versatile late-stage diversifications. Also described is the first manganese-catalyzed C-H activation in continuous flow, thus enabling efficient hydroarylations within only 20 minutes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Iridium/Bipyridine-Catalyzed ortho-Selective C-H Borylation of Phenol and Aniline Derivatives.

    Science.gov (United States)

    Li, Hong-Liang; Kanai, Motomu; Kuninobu, Yoichiro

    2017-11-03

    An iridium-catalyzed ortho-selective C-H borylation of phenol and aniline derivatives has been successfully developed. Iridium/bipyridine-catalyzed C-H borylation generally occurred at the meta- and para-positions of aromatic substrates. Introduction of an electron-withdrawing substituent on the bipyridine-type ligand and a methylthiomethyl group on the hydroxy and amino groups of the phenol and aniline substrates, however, dramatically altered the regioselectivity, affording exclusively ortho-borylated products. The reaction proceeded in good to excellent yields with good functional group tolerance. C-H borylation was applied to the synthesis of a calcium receptor modulator.

  3. Valuing Convertible Bonds Based on LSRQM Method

    Directory of Open Access Journals (Sweden)

    Jian Liu

    2014-01-01

    Full Text Available Convertible bonds are one of the essential financial products for corporate finance, while the pricing theory is the key problem to the theoretical research of convertible bonds. This paper demonstrates how to price convertible bonds with call and put provisions using Least-Squares Randomized Quasi-Monte Carlo (LSRQM method. We consider the financial market with stochastic interest rates and credit risk and present a detailed description on calculating steps of convertible bonds value. The empirical results show that the model fits well the market prices of convertible bonds in China’s market and the LSRQM method is effective.

  4. Medium effects on a C-H bond fission reaction. Solvent and salt effects on the solvolysis of arylsulfonylmethyl perchlorates.

    NARCIS (Netherlands)

    Menninga, Lubbertus

    1976-01-01

    In this thesis, medium effects on the general basecatelyzed solvolysis of two arylsulfonylmethyl perchlorates are described and analyzed in some detail. For the aqueous media, special attention is given to possible effects due to changes in diffusionally averaged water structure. ... Zie: Summary

  5. Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan

    2007-07-18

    A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.

  6. Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

    DEFF Research Database (Denmark)

    Eriksen, J.; Monsted, L.; Monsted, O.

    2010-01-01

    The mechanism of the catalytic HID exchange in primary alcohol substrates derived from aldopentoses, promoted by a macrocyclic rhodium(III) complex, has been shown to occur by a reversible redox reaction that gives aldehyde and a rhodium hydride complex. Hydride exchange in the latter complex...... promotes the introduction of solvent hydrogen in the primary alcohol formed by the reverse reaction. The hydride complex has been crystallographically characterized as a trifluoromethanesulfonate salt that contains the trans-[Rh(cycb)(H)(OH2)](2+) (cycb = rac-5,5,7,12,12,14-hexamethyl-1......,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

  7. Regioselective C2 Oxidative Olefination of Indoles and Pyrroles through Cationic Rhodium(III)-Catalyzed C-H Bond Activation.

    Science.gov (United States)

    Li, Bin; Ma, Jianfeng; Xie, Weijia; Song, Haibin; Xu, Shansheng; Wang, Baiquan

    2013-09-02

    Be economic with your atoms! An efficient Rh-catalyzed oxidative olefination of indoles and pyrroles with broad substrate scope and tolerance is reported. The catalytic reaction proceeds with excellent regio- and stereoselectivity. The directing group N,N-dimethylcarbamoyl was crucial for the reaction and could be removed easily. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

    Science.gov (United States)

    Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

    2018-05-14

    Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. The preparation and mechanical properties of Al-containing a-C : H thin films

    International Nuclear Information System (INIS)

    Zhang Guangan; Yan Pengxun; Wang Peng; Chen Youming; Zhang Junyan

    2007-01-01

    Al-containing hydrogenated amorphous carbon (Al-C : H) films were deposited on silicon substrates using a mid frequency magnetron sputtering Al target in an argon and methane gas mixture. The composition, surface morphology, hardness and friction coefficient of the films were characterized using x-ray photoelectron spectroscopy, atomic force microscopy, nanoindentation and tribological tester. The Al-C : H films deposited at low CH 4 content show high surface roughness, low hardness and high friction coefficient, similar to metallic Al films; in contrast, the Al-C : H films prepared under high CH 4 content indicate low surface roughness, high hardness and low friction coefficient, close to that of hard a-C : H films as wear-resistance films

  10. Advanced TiC/a-C: H nanocomposite coatings deposited by magnetron sputtering

    OpenAIRE

    Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De; Strondl, C.

    2006-01-01

    TiC/a-C:H nanocomposite coatings have been deposited by magnetron Sputtering. They consist of 2-5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a Columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing substrate bias or carbon content. Micro-cracks induced by nanoindentation or wear tests readily propagate through the column boundaries whereas the coatings without a columnar inicrostructure exhibit s...

  11. Rhodium-catalyzed C-H functionalization with N-acylsaccharins.

    Science.gov (United States)

    Wu, Hongxiang; Liu, Tingting; Cui, Ming; Li, Yue; Jian, Junsheng; Wang, Hui; Zeng, Zhuo

    2017-01-18

    A rhodium-catalyzed C-H functionalization with activated amides by decarbonylation has been developed. Notably, this is the first C-H arylation employing N-acylsaccharins as coupling partners to give biaryls in good to excellent yields. The highlight of the work is the high tolerance of functional groups such as formyl, ester, and vinyl and the use of a removable directing group.

  12. Palladium catalyzed selective distal C-H olefination of biaryl systems.

    Science.gov (United States)

    Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata

    2016-11-29

    Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

  13. Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols

    KAUST Repository

    Ranjit, Sadananda

    2011-11-04

    We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na 2CO 3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. © 2011 American Chemical Society.

  14. The mechanism of stereospecific C-H oxidation by Fe(Pytacn) complexes: bioinspired non-heme iron catalysts containing cis-labile exchangeable sites.

    Science.gov (United States)

    Prat, Irene; Company, Anna; Postils, Verònica; Ribas, Xavi; Que, Lawrence; Luis, Josep M; Costas, Miquel

    2013-05-17

    A detailed mechanistic study of the hydroxylation of alkane C-H bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [Fe(II)(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the α and γ positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The C-H hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that C-H hydroxylation is performed by highly electrophilic [Fe(V)(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the C-H bond, followed by rebound of the hydroxyl ligand. The [Fe(V)(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the α substituent of the pyridine, and this reactivity behavior is rationalized by computational methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  16. The radiosensitivity of human keratinocytes: influence of activated c-H-ras oncogene expression and tumorigenicity

    International Nuclear Information System (INIS)

    Mendonca, M.S.; Redpath, J.L.; Stanbridge, E.J.

    1991-01-01

    The authors investigated γ-ray sensitivity of several activated c-H-ras (EJ) containing clones established after transfection of the spontaneously immortalized non-tumorigenic human keratinocyte cell line HaCaT. The clones were grouped according to tumorigenic potential after subcutaneous injection into nude mice, and fell into three classes: Class I clones A-4 and I-6 are non-tumorigenic and express very low levels of c-H-ras mRNA and no mutated ras protein (p 21 ); Class II clones I-5 and I-7 grow to large (benign) epidermal cysts, express intermediate to high c-H-ras mRNA and variable levels of mutated ras p 21 protein with clone I-5 expressing little and clone I-7 expressing high levels of p 21 ; Class III clones II-3 and II-4 grow to solid squamous cell carcinomas, express high c-H-ras mRNA and high level of mutated p 21 ras protein similar to clone I-7. Comparison of single-hit multitarget or linear-quadratic survival curve parameters, and survival at 2Gy (S 2 ) indicate no general correlation with either activated c-H-ras expression level or tumorigenic potential, and increased radioresistance. (author)

  17. Monte Carlo Simulations of Phosphate Polyhedron Connectivity in Glasses

    Energy Technology Data Exchange (ETDEWEB)

    ALAM,TODD M.

    1999-12-21

    Monte Carlo simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional exchange and double-quantum NMR experiments of phosphate glasses. These Monte Carlo simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.

  18. On the origin of red and blue shifts of X-H and C-H stretching vibrations in formic acid (formate ion) and proton donor complexes.

    Science.gov (United States)

    Tâme Parreira, Renato Luis; Galembeck, Sérgio Emanuel; Hobza, Pavel

    2007-01-08

    Complexes between formic acid or formate anion and various proton donors (HF, H(2)O, NH(3), and CH(4)) are studied by the MP2 and B3LYP methods with the 6-311++G(3df,3pd) basis set. Formation of a complex is characterized by electron-density transfer from electron donor to ligands. This transfer is much larger with the formate anion, for which it exceeds 0.1 e. Electron-density transfer from electron lone pairs of the electron donor is directed into sigma* antibonding orbitals of X--H bonds of the electron acceptor and leads to elongation of the bond and a red shift of the X--H stretching frequency (standard H-bonding). However, pronounced electron-density transfer from electron lone pairs of the electron donor also leads to reorganization of the electron density in the electron donor, which results in changes in geometry and vibrational frequency. These changes are largest for the C--H bonds of formic acid and formate anion, which do not participate in H-bonding. The resulting blue shift of this stretching frequency is substantial and amounts to almost 35 and 170 cm(-1), respectively.

  19. Compositional, structural and mechanical characteristics of nc-TiC/a-C:H nanocomposite films

    International Nuclear Information System (INIS)

    Wang Yaohui; Zhang Xu; Wu Xianying; Zhang Huixing; Zhang Xiaoji

    2008-01-01

    Nanocomposite nc-TiC/a-C:H films, with an unusual combination of superhardness, high elastic modulus and high elastic recovery, are prepared by filtered cathodic vacuum arc technique using the C 2 H 2 gas as the precursor. The effects of filter coil current on compositional, structural and mechanical properties of the nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. XPS and Raman analyses show that composition and nanostructure of the nc-TiC/a-C:H films can be changed by varying the filter coil current. By selecting the proper value of filter coil current, 2.5 A, one can remarkably enhance the mechanical properties of films such as superhardness (43.6 GPa). The superhardness can be ascribed to the phase variation and the nanostructure.

  20. DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex

    KAUST Repository

    Lee, Richmond

    2017-01-17

    Mechanistic insights into the selective C-H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using Bader’s atom in molecules (AIM) analysis on the elementary steps of the hydrogen transfer process, TS1 and TS2, it was observed that the calculated H-transfer models were closely similar to Hall’s metal-assisted σ-bond metathesis through bond critical point (BCP) comparisons. One distinguishable feature was the fact that the formal oxidation state of the W changed in the concerted H-transfer process. To better differentiate, we term these processes as ‘Formal Reductive Hydrogen Transfer’ (FRHT) for TS1 and ‘Formal Oxidative Hydrogen Transfer’ (FOHT) for TS2.

  1. DFT Mechanistic Study of the Selective Terminal C-H Activation of n-Pentane with a Tungsten Allyl Nitrosyl Complex

    KAUST Repository

    Lee, Richmond; Tan, Davin; Liu, Chaoli; Li, Huaifeng; Guo, Hao; Shyue, Jing-Jong; Huang, Kuo-Wei

    2017-01-01

    Mechanistic insights into the selective C-H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using Bader’s atom in molecules (AIM) analysis on the elementary steps of the hydrogen transfer process, TS1 and TS2, it was observed that the calculated H-transfer models were closely similar to Hall’s metal-assisted σ-bond metathesis through bond critical point (BCP) comparisons. One distinguishable feature was the fact that the formal oxidation state of the W changed in the concerted H-transfer process. To better differentiate, we term these processes as ‘Formal Reductive Hydrogen Transfer’ (FRHT) for TS1 and ‘Formal Oxidative Hydrogen Transfer’ (FOHT) for TS2.

  2. Oxidative C-H activation of amines using protuberant lychee-like goethite

    Science.gov (United States)

    Goethite with protuberant lychee morphology has been synthesized that accomplishes C-H activation of N-methylanilines to generate α-aminonitriles; the catalyst takes oxygen from air and uses it as a cooxidant in the process. Inspired by nature, we aspired to design a protocol for...

  3. Silver-mediated oxidative C-H difluoromethylation of phenanthridines and 1,10-phenanthrolines.

    Science.gov (United States)

    Zhu, Sheng-Qing; Xu, Xiu-Hua; Qing, Feng-Ling

    2017-10-17

    A silver-mediated oxidative difluoromethylation of phenanthridines and 1,10-phenanthrolines with TMSCF 2 H is disclosed. This C-H difluoromethylation of N-containing polycyclic aromatics constitutes an efficient method for the regioselective synthesis of difluoromethylated N-heterocycles.

  4. Transition metal catalyzed C-H activation for the synthesis of ...

    Indian Academy of Sciences (India)

    DEBJIT BASU

    2018-06-14

    Jun 14, 2018 ... construction of biaryls, which are considered to be the important ... The quest that gained significance over the period of time is to develop .... tic pathway that involve a directed C-H activation.20 This methodology was later ...

  5. Preparation and comparison of a-C:H coatings using reactive sputter techniques

    Energy Technology Data Exchange (ETDEWEB)

    Keunecke, M., E-mail: martin.keunecke@ist.fraunhofer.d [Fraunhofer Institute for Surface Engineering and Thin Films (IST), Braunschweig (Germany); Weigel, K.; Bewilogua, K. [Fraunhofer Institute for Surface Engineering and Thin Films (IST), Braunschweig (Germany); Cremer, R.; Fuss, H.-G. [CemeCon AG, Wuerselen (Germany)

    2009-12-31

    Amorphous hydrogenated carbon (a-C:H) coatings are widely used in several industrial applications. These coatings commonly will be prepared by plasma activated chemical vapor deposition (PACVD). The main method used to prepare a-C:H coating in industrial scale is based on a glow discharge in a hydrocarbon gas like acetylene or methane using a substrate electrode powered with medium frequency (m.f. - some 10 to 300 kHz). Some aims of further development are adhesion improvement, increase of hardness and high coating quality on complex geometries. A relatively new and promising technique to fulfil these requirements is the deposition of a-C:H coatings by a reactive d.c. magnetron sputter deposition from a graphite target with acetylene as reactive gas. An advancement of this technique is the deposition in a pulsed magnetron sputter process. Using these three mentioned techniques a-C:H coatings were prepared in the same deposition machine. For adhesion improvement different interlayer systems were applied. The effect of different substrate bias voltages (d.c. and d.c. pulse) was investigated. By applying the magnetron sputter technique in the d.c. pulse mode, plastic hardness values up to 40 GPa could be reached. Besides hardness other mechanical properties like resistance against abrasive wear were measured and compared. Cross sectional SEM images showed the growth structure of the coatings.

  6. Late-stage diversification of biologically active pyridazinones via a direct C-H functionalization strategy.

    Science.gov (United States)

    Li, Wei; Fan, Zhoulong; Geng, Kaijun; Xu, Youjun; Zhang, Ao

    2015-01-14

    Divergent C-H functionalization reactions (arylation, carboxylation, olefination, thiolation, acetoxylation, halogenation, naphthylation) using a pyridazinone moiety as an internal directing group were successfully established. This approach offers a late-stage, ortho-selective diversification of a biologically active pyridazinone scaffold. Seven series of novel pyridazinone analogues were synthesized conveniently as the synthetic precursors of potential sortase A (SrtA) inhibitors.

  7. Bioorthogonal Diversification of Peptides through Selective Ruthenium(II)-Catalyzed C-H Activation.

    Science.gov (United States)

    Schischko, Alexandra; Ren, Hongjun; Kaplaneris, Nikolaos; Ackermann, Lutz

    2017-02-01

    Methods for the chemoselective modification of amino acids and peptides are powerful techniques in biomolecular chemistry. Among other applications, they enable the total synthesis of artificial peptides. In recent years, significant momentum has been gained by exploiting palladium-catalyzed cross-coupling for peptide modification. Despite major advances, the prefunctionalization elements on the coupling partners translate into undesired byproduct formation and lengthy synthetic operations. In sharp contrast, we herein illustrate the unprecedented use of versatile ruthenium(II)carboxylate catalysis for the step-economical late-stage diversification of α- and β-amino acids, as well as peptides, through chemo-selective C-H arylation under racemization-free reaction conditions. The ligand-accelerated C-H activation strategy proved water-tolerant and set the stage for direct fluorescence labelling as well as various modes of peptide ligation with excellent levels of positional selectivity in a bioorthogonal fashion. The synthetic utility of our approach is further demonstrated by twofold C-H arylations for the complexity-increasing assembly of artificial peptides within a multicatalytic C-H activation manifold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. F. H. C h . J othmann , De Bijbel in de loop der eeuwen. Kampen, J ...

    African Journals Online (AJOL)

    Test

    F. H. C h . J othmann , De Bijbel in de loop der eeuwen. Kampen, J . H. Kok. N.V., 1954, 43 bis. Prys 95 cent. Hierdie werkie geskryf vir gebruik op skool, kategesasie en jeug- vereniging is besonder smakelik versorg met uiters insiggewende illu- strasies oor die geskiedenis van die Bybel as geskrif en boek. Die stof is.

  9. Breakdown of the Coulomb friction law in TiC/a-C:H nanocomposite coatings

    International Nuclear Information System (INIS)

    Pei, Y. T.; Huizenga, P.; Galvan, D.; Hosson, J. Th. M. de

    2006-01-01

    Advanced TiC/a-C:H nanocomposite coatings have been produced via reactive deposition in a closed-field unbalanced magnetron sputtering system (Hauzer HTC-1000 or HTC 1200). In this paper, we report on the tribological behavior of TiC/a-C:H nanocomposite coatings in which ultralow friction is tailored with superior wear resistance, two properties often difficult to achieve simultaneously. Tribotests have been performed at room temperature with a ball-on-disk configuration. In situ monitoring of the wear depth of the coated disk together with the wear height of the ball counterpart at nanometer scale reveals that the self-lubricating effects are induced by the formation of transfer films on the surface of the ball counterpart. A remarkable finding is a breakdown of the Coulomb friction law in the TiC/a-C:H nanocomposite coatings. In addition, the coefficient of friction of TiC/a-C:H nanocomposite coatings decreases with decreasing relative humidity. A superior wear resistance of the coated disk at a level of 10 -17 m 3 /N m (per lap) has been achieved under the condition of superlow friction and high toughness, both of which require fine TiC nanoparticles (e.g., 2 nm) and a wide matrix separation that must be comparable to the dimensions of the nanoparticles

  10. High growth rate of a-SiC:H films using ethane carbon source by HW

    Indian Academy of Sciences (India)

    Hydrogenated amorphous silicon carbide (a-SiC:H) thin films were prepared ... Total hydrogen content drops from 22.6 to 14.4 at.% when deposition pressure is increased. Raman spectra show increase in structural disorder with increase in ...

  11. Rhodium Catalyzed Annulation of N-Benzoylsulfonamide with Isocyanide via C-H Activation

    Science.gov (United States)

    Zhu, Chen; Xie, Weiqing; Falck, John R.

    2012-01-01

    Isocyanide insertion: the first rhodium-catalyzed annulation of N-benzoylsulfonamide incorporating with isocyanide via C-H activation is described. The transformation is broadly compatible with N-benzoylsulfonamides bearing various electron-properties as well as isocyanides. From practical point of view, this methodology provides the most straightforward approach to a series of 3-(imino)isoindolinones. PMID:21972033

  12. Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes.

    Science.gov (United States)

    Manoharan, Ramasamy; Sivakumar, Ganesan; Jeganmohan, Masilamani

    2016-08-18

    A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

  13. Electrochemically induced C-H functionalization using bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl dual redox catalysts in a two-phase electrolytic system

    International Nuclear Information System (INIS)

    Li, Chao; Zeng, Cheng-Chu; Hu, Li-Ming; Yang, Feng-Lin; Yoo, Seung Joon; Little, R. Daniel

    2013-01-01

    Highlights: •Electrocatalytic C-H bond functionalization of tetrahydroisoquinolines is reported. •The transformation is mediated by a bromide ion/TEMPO dual redox catalyst system. •The transformation is conducted in a two-phase electrolytic medium. •The mechanism is proposed to proceed via a sequence of oxidation and addition reactions involving water as a nucleophile. •The procedure features wide substrate scope, the use of mild reaction conditions. -- Abstract: The electrochemical oxidative functionalization of benzylic C-H bonds, mediated by a dual bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) redox catalyst system in a two-phase electrolytic medium, has been explored using cyclic voltammetry (CV) and preparative electrolysis techniques. The results show that electron transfer between TEMPO + and a neutral substrate occurs with an efficiency that depends upon the presence of a base. The preparative scale electrolysis led to the formation of dihydro-isoquinolinones, isochromanone and xanthenone in moderate to excellent yields. On the basis of the CV analysis and preparative electrolysis results, a reaction mechanism is proposed

  14. Double C-H activation of ethane by metal-free SO2*+ radical cations.

    Science.gov (United States)

    de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

    2010-06-01

    The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

  15. Electrochemistry of transition metal complex catalysts Part 10. Intra- and intermolecular electrochemically activated C-H addition to the central metal atom of a P-C-P-pincer iridium complex

    International Nuclear Information System (INIS)

    Novak, Filip; Speiser, Bernd; Mohammad, Hani A.Y.; Mayer, Hermann A.

    2004-01-01

    The electrochemical properties of a promising catalyst for C-H bond activation are investigated. This P-C-P-pincer complex of iridium exhibits an intramolecular C-H oxidative addition at room temperature, which becomes enhanced upon oxidation. The reaction product is detected by cyclic voltammetry. Mechanistic, kinetic, and thermodynamic information is extracted from experiments in combination with digital simulation. Multicycle voltammograms and voltammograms of mixtures consistently suggest an extended square scheme as the electrode reaction mechanism. The unsubstituted parent compound shows a more complex redox behavior including a coupled ECE sequence. Intermolecular C-H activation by reaction of the complex in the presence of cyclooctane is indicated by characteristic changes in the cyclic voltammograms

  16. Deposition of a-C:H films on a nanotrench pattern by bipolar PBII and D

    International Nuclear Information System (INIS)

    Hirata, Yuki; Nakahara, Yuya; Nagato, Keisuke; Choi, Junho

    2016-01-01

    In this study, hydrogenated amorphous carbon (a-C:H) films were deposited on a nanotrench pattern (300 nm pitch, aspect ratio: 2.0) by bipolar-type plasma based ion implantation and deposition technique (bipolar PBII and D), and the effects of bipolar pulse on the film properties were investigated. Moreover, the behaviour of ions and radicals surrounding the nanotrench was analyzed to clarify the coating mechanism and properties of the a-C:H films on the nanotrench. Further, thermal nanoimprint lithography was carried out using the nanotrench pattern coated with a-C:H films as the mold, and the mold release properties were evaluated. All nanotrench surfaces were successfully coated with the a-C:H films, but the film thickness on the top, sidewall, and bottom surfaces of the trench were not uniform. The surface roughness of the a-C:H films was found to decrease at a higher positive voltage; this happens due to the higher electron temperature around the nanotrench because of the surface migration of plasma particles arrived on the trench. The effects of the negative voltage on the behaviour of ions and radicals near the sidewall of the nanotrench are quite similar to those near the microtrench reported previously (Park et al 2014 J. Phys. D: Appl. Phys . 47 335306). However, the positive pulse voltage was also found to affect the behaviour of ions and radicals near the sidewall surface. The incident angles of ions on the sidewall surface increased with the positive pulse voltage because the energy of incoming ions on the trench decreases with increasing positive voltage. Moreover, the incident ion flux on the sidewall is affected by the positive voltage history. Further, the radical flux decreases with increasing positive voltage. It can be concluded that a higher positive voltage at a lower negative voltage condition is good to obtain better film properties and higher film thickness on the sidewall surface. Pattern transfer properties for the nanoimprint formed by

  17. Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

    Science.gov (United States)

    Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

    2018-01-26

    The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A Modular Flow Design for the meta-Selective C-H Arylation of Anilines.

    Science.gov (United States)

    Gemoets, Hannes P L; Laudadio, Gabriele; Verstraete, Kirsten; Hessel, Volker; Noël, Timothy

    2017-06-12

    Described herein is an effective and practical modular flow design for the meta-selective C-H arylation of anilines. The design consists of four continuous-flow modules (i.e., diaryliodonium salt synthesis, meta-selective C-H arylation, inline copper extraction, and aniline deprotection) which can be operated either individually or consecutively to provide direct access to meta-arylated anilines. With a total residence time of 1 hour, the desired product could be obtained in high yield and excellent purity without the need for column chromatography, and the residual copper content meets the standards for parenterally administered pharmaceutical substances. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  19. Platinum containing amorphous hydrogenated carbon (a-C:H/Pt) thin films as selective solar absorbers

    International Nuclear Information System (INIS)

    Lan, Yung-Hsiang; Brahma, Sanjaya; Tzeng, Y.H.; Ting, Jyh-Ming

    2014-01-01

    We have investigated a double-cermet structured thin film in which an a-C:H thin film was used as an anti-reflective (AR) layer and two platinum-containing amorphous hydrogenated carbon (a-C:H/Pt) thin films were used as the double cermet layers. A reactive co-sputter deposition method was used to prepare both the anti-reflective and cermet layers. Effects of the target power and heat treatment were studied. The obtained films were characterized using X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy. The optical absorptance and emittance of the as deposited and annealed films were determined using UV–vis-NIR spectroscopy. We show that the optical absorptance of the resulting double-cermet structured thin film is as high as 96% and remains to be 91% after heat treatment at 400 °C, indicating the thermal stability of the film

  20. Iodine(III)-Mediated Selective Intermolecular C-H Amination for the Chemical Diversification of Tryptamines.

    Science.gov (United States)

    Bosnidou, Alexandra E; Millán, Alba; Ceballos, Javier; Martínez, Claudio; Muñiz, Kilian

    2016-08-05

    Defined hypervalent iodine reagents of the general structure PhI[N(SO2R)(SO2R')]2 promote the selective direct C-H-amination of the indole core of various tryptamines. Starting from a general C2-amination strategy, subsequent transformations enable a variety of site-selective functionalizations, which proceed with noteworthy high chemoselectivity and provide an overall access to structurally diversified products.

  1. Visible-light-promoted redox neutral C-H amidation of heteroarenes with hydroxylamine derivatives.

    Science.gov (United States)

    Qin, Qixue; Yu, Shouyun

    2014-07-03

    A room temperature redox neutral direct C-H amidation of heteroarenes has been achieved. Hydroxylamine derivatives, which are easily accessed, have been employed as tunable nitrogen sources. These reactions were enabled by a visible-light-promoted single-electron transfer pathway without a directing group. A variety of heteroarenes, such as indoles, pyrroles, and furans, could go through this amidation with high yields (up to 98%). These reactions are highly regioselective, and all the products were isolated as a single regioisomer.

  2. Studies of beauty baryon decays to D 0 p h - And Λ c + h - Final states

    NARCIS (Netherlands)

    Aaij, R.; Adeva, B.; Adinolfi, M.; Adrover, C.; Affolder, A.; Ajaltouni, Z.; Albrecht, J.; Alessio, F.; Alexander, M.; Ali, S.; Alkhazov, G.; Alvarez Cartelle, P.; Alves, A. A.; Amato, S.; Amerio, S.; Amhis, Y.; Anderlini, L.; Anderson, J.; Andreassen, P.R.; Andreotti, M.; Andrews, J.E.; Appleby, R. B.; Aquines Gutierrez, O.; Archilli, F.; Artamonov, A.; Artuso, M.; Aslanides, E.; Auriemma, G.; Baalouch, M.; Bachmann, S.; Back, J. J.; Badalov, A.; Balagura, V.; Baldini, W.; Barlow, R. J.; Barschel, C.; Barsuk, S.; Barter, W.; Batozskaya, V.; Bauer, Th.; Bay, A.; Beddow, J.; Bedeschi, F.; Bediaga, I.; Belogurov, S.; Belous, K.; Belyaev, I.; Ben-Haim, E.; Bencivenni, G.; Benson, S.; Benton, J.; Berezhnoy, A.; Bernet, R.; Bettler, M-O.; Van Beuzekom, Martin; Bien, A.; Bifani, S.; Bird, T.D.; Bizzeti, A.; Bjørnstad, P. M.; Blake, T.; Blanc, F.; Blouw, J.; Blusk, S.; Bocci, V.; Bondar, A.; Bondar, N.; Bonivento, W.; Borghi, S.; Borgia, A.; Bowcock, T. J. V.; Bowen, E.; Bozzi, C.; Brambach, T.; Van Den Brand, J.; Bressieux, J.; Brett, D.; Britsch, M.; Britton, T.; Brook, N. H.; Brown, H.; Bursche, A.; Busetto, G.; Buytaert, J.; Cadeddu, S.; Calabrese, R.; Callot, O.; Calvi, M.; Calvo Gomez, M.; Camboni, A.; Campana, P.; Campora Perez, D.; Carbone, A.; Carboni, G.; Cardinale, R.; Cardini, A.; Carranza-Mejia, H.; Carson, L.; Carvalho Akiba, K.; Casse, G.; Castillo Garcia, L.; Cattaneo, M.; Cauet, Ch; Cenci, R.; Charles, M.; Charpentier, Ph; Cheung, S-F.; Chiapolini, N.; Chrzaszcz, M.; Ciba, K.; Cid Vidal, X.; Ciezarek, G.; Clarke, P. E. L.; Clemencic, M.; Cliff, H. V.; Closier, J.; Coca-Pelaz, A.; Coco, V.; Cogan, J.; Cogneras, E.; Collins, P.; Comerma-Montells, A.; Contu, A.; Cook, A.; Coombes, M.; Coquereau, S.; Corti, G.; Couturier, B.; Cowan, G. A.; Craik, D. C.; Cruz Torres, M.; Cunliffe, S.; Currie, C.R.; D'Ambrosio, C.; Dalseno, J.; David, P.; David, P. N Y; Davis, A.; De Bonis, I.; De Bruyn, K.; De Capua, S.; De Cian, M.; de Miranda, J. M.; Paula, L.E.; da-Silva, W.S.; De Simone, P.; Decamp, D.; Deckenhoff, M.; Del Buono, L.; Déléage, N.; Derkach, D.; Deschamps, O.; Dettori, F.; Di Canto, A.; Dijkstra, H.; Dogaru, M.; Donleavy, S.; Dordei, F.; Dorosz, P.; Dosil Suárez, A.; Dossett, D.; Dovbnya, A.; Dupertuis, F.; Durante, P.; Dzhelyadin, R.; Dziurda, A.; Dzyuba, A.; Easo, S.; Egede, U.; Egorychev, V.; Eidelman, S.; Van Eijk, D.; Eisenhardt, S.; Eitschberger, U.; Ekelhof, R.; Eklund, L.; El Rifai, I.; Elsasser, Ch.; Falabella, A.; Färber, C.; Farinelli, C.; Farry, S.; Ferguson, D.; Fernandez Albor, V.; Ferreira Rodrigues, F.; Ferro-Luzzi, M.; Filippov, S.; Fiore, M.; Fiorini, M.; Fitzpatrick, C.; Fontana, Mark; Fontanelli, F.; Forty, R.; De Aguiar Francisco, O.; Frank, M.; Frei, C.; Frosini, M.; Furfaro, E.; Gallas Torreira, A.; Galli, D.; Gandelman, M.; Gandini, P.; Gao, Y.; Garofoli, J.; Garosi, P.; Garra Tico, J.; Garrido, L.; Carvalho-Gaspar, M.; Gauld, Rhorry; Gersabeck, E.; Gersabeck, M.; Gershon, T. J.; Ghez, Ph; Gibson, V.; Giubega, L.; Gligorov, V. V.; Göbel, C.; Golubkov, D.; Golutvin, A.; Gomes, A.Q.; Head-Gordon, Teresa; Grabalosa Gándara, M.; Graciani Diaz, R.; Granado Cardoso, L. A.; Graugés, E.; Graziani, G.; Grecu, A.; Greening, E.; Gregson, S.; Griffith, P.; Grillo, L.; Grünberg, O.; Gui, B.; Gushchin, E.; Guz, Yu; Gys, T.; Hadjivasiliou, C.; Haefeli, G.; Haen, C.; Hafkenscheid, T. W.; Haines, S. C.; Hall, S.; Hamilton, B.; Hampson, T.; Hansmann-Menzemer, S.; Harnew, N.; Harnew, S. T.; Harrison, J.; Hartmann, T.; He, J.; Head, T.; Heijne, V.; Hennessy, K.; Henrard, P.; Hernando Morata, J. A.; van Herwijnen, E.; Heß, M.; Hicheur, A.; Hicks, G.E.; Hill, D.; Hoballah, M.; Hombach, C.; Hulsbergen, W.; Hunt, P.; Huse, J.T.; Hussain, N.; Hutchcroft, D. E.; Hynds, D.; Iakovenko, V.; Idzik, M.; Ilten, P.; Jacobsson, R.; Jaeger, A.; Jans, E.; Jaton, P.; Jawahery, A.; Jing, F.; John, M.; Johnson, D.; Jones, C. R.; Joram, C.; Jost, B.; Jurik, N.; Kaballo, M.; Kandybei, S.; Kanso, W.; Karacson, M.; Karbach, T. M.; Kenyon, I. R.; Ketel, T.; Khanji, B.; Klaver, S.M.; Kochebina, O.; Komarov, I.; Koopman, R. F.; Koppenburg, P.; Korolev, M.; Kozlinskiy, A.; Kravchuk, L.; Kreplin, K.; Kreps, M.; Krocker, G.; Krokovny, P.; Kruse, F.; Kucharczyk, M.; Kudryavtsev, V.; Kurek, K.; Kvaratskheliya, T.; La Thi, V. N.; Lacarrere, D.; Lafferty, G. D.; Lai, A.; Lambert, D.M.; Lambert, R. W.; Lanciotti, E.; Lanfranchi, G.; Langenbruch, C.; Latham, T. E.; Lazzeroni, C.; Le Gac, R.; Van Leerdam, J.; Lees, J. P.; Lefèvre, R.; Leflat, A.; Lefrançois, J.; Di Leo, S.; Leroy, O.; Lesiak, T.; Leverington, B.; Li, Y.; Li Gioi, L.; Liles, M.; Lindner, R.; Linn, S.C.; Lionetto, F.; Liu, B.; Liu, G.; Lohn, S.; Longstaff, I.; Lopes, J. H.; Lopez-March, N.; Lu, H.; Lucchesi, D.; Luisier, J.; Luo, H.; Luppi, E.; Lupton, O.; Machefert, F.; Machikhiliyan, I. V.; Maciuc, F.; Maev, O.; Malde, S.; Manca, G.; Mancinelli, G.; Maratas, J.; Marconi, U.; Marino, P.; Märki, R.; Marks, J.; Martellotti, G.; Martens, A.; Martín Sánchez, A.; Martinelli-Boneschi, F.; Martinez-Santos, D.; Martins Tostes, D.; Martynov, A.; Massafferri, A.; Matev, R.; Mathe, Z.; Matteuzzi, C.; Maurice, E.; Mazurov, A.; McCann, M.; McCarthy, J.; Mcnab, A.; McNulty, R.; McSkelly, B.; Meadows, B. T.; Meier, F.; Meissner, M.; Merk, M.; Milanes, D. A.; Minard, M. N.; Molina Rodriguez, J.; Monteil, S.; Moran-Zenteno, D.; Morawski, P.; Mordà, A.; Morello, M. J.; Mountain, R.; Mous, I.; Muheim, F.; Müller, Karl; Muresan, R.; Muryn, B.; Muster, B.; Naik, P.; Nakada, T.; Nandakumar, R.; Nasteva, I.; Needham, M.; Neubert, S.; Neufeld, N.; Nguyen, A. D.; Nguyen, T. D.; Nguyen-Mau, C.; Nicol, M.; Niess, V.; Niet, R.; Nikitin, N.; Nikodem, T.; Nomerotski, A.; Novoselov, A.; Oblakowska-Mucha, A.; Obraztsov, V.; Oggero, S.; Ogilvy, S.; Okhrimenko, O.; Oldeman, R.; Onderwater, G.; Orlandea, M.; Otalora Goicochea, J. M.; Owen, R.P.; Oyanguren, A.; Pal, B. K.; Palano, A.; Palutan, M.; Panman, J.; Papanestis, A.; Pappagallo, M.; Pappalardo, L.L.; Parkes, C.; Parkinson, C. J.; Passaleva, G.; Patel, G. D.; Patel, M.; Patrignani, C.; Pavel-Nicorescu, C.; Pazos Alvarez, A.; Pearce, D.A.; Pellegrino, A.; Penso, G.; Pepe Altarelli, M.; Perazzini, S.; Perez Trigo, E.; Pérez-Calero Yzquierdo, A.; Perret, P.; Perrin-Terrin, M.; Pescatore, L.; Pesen, E.; Pessina, G.; Petridis, K.; Petrolini, A.; Picatoste Olloqui, E.; Pietrzyk, B.; Pilař, T.; Pinci, D.; Playfer, S.; Plo Casasus, M.; Polci, F.; Polok, G.; Poluektov, A.; Polycarpo, E.; Popov, A.; Popov, D.; Popovici, B.; Potterat, C.; Powell, A.; Prisciandaro, J.; Pritchard, C.A.; Prouve, C.; Pugatch, V.; Puig Navarro, A.; Punzi, G.; Qian, Y.W.; Rachwal, B.; Rademacker, J. H.; Rakotomiaramanana, B.; Rangel, M. S.; Raniuk, I.; Rauschmayr, N.; Raven, G.; Redford, S.; Reichert, S.; Reid, M.; dos Reis, A. C.; Ricciardi, S.; Richards, Al.; Rinnert, K.; Rives Molina, V.; Roa Romero, D. A.; Robbe, P.; Roberts, D. A.; Rodrigues, A. B.; Rodrigues, L.E.T.; Rodriguez Perez, P.; Roiser, S.; Romanovsky, V.; Romero Vidal, A.; Rotondo, M.; Rouvinet, J.; Ruf, T.; Ruffini, F.; Ruiz, van Hapere; Ruiz Valls, P.; Sabatino, G.; Saborido Silva, J. J.; Sagidova, N.; Sail, P.; Saitta, B.; Salustino Guimaraes, V.; Sanmartin Sedes, B.; Santacesaria, R.; Santamarina Rios, C.; Santovetti, E.; Sapunov, M.; Sarti, A.; Satriano, C.; Satta, A.; Savrie, M.; Savrina, D.; Schiller, M.; Schindler, R. H.; Schlupp, M.; Schmelling, M.; Schmidt, B.; Schneider, O.; Schopper, A.; Schune, M. H.; Schwemmer, R.; Sciascia, B.; Sciubba, A.; Seco, M.; Semennikov, A.; Senderowska, K.; Sepp, I.; Serra, N.; Serrano, J.; Seyfert, P.; Shapkin, M.; Shapoval, I.; Shcheglov, Y.; Shears, T.; Shekhtman, L.; Shevchenko, O.; Shevchenko, V.; Shires, A.; Silva Coutinho, R.; Sirendi, M.; Skidmore, N.; Skwarnicki, T.; Smith, N. A.; Smith, E.; Smith, E.; Smith, J; Smith, M.; Sokoloff, M. D.; Soler, F. J. P.; Soomro, F.; de Souza, D.K.; Souza De Paula, B.; Spaan, B.; Sparkes, A.; Spradlin, P.; Stagni, F.; Stahl, S.; Steinkamp, O.; Stevenson-Moore, P.; Stoica, S.; Stone, S.; Storaci, B.; Stracka, S.; Straticiuc, M.; Straumann, U.; Subbiah, V. K.; Sun, L.; Sutcliffe, W.; Swientek, S.; Syropoulos, V.; Szczekowski, M.; Szczypka, P.; Szilard, D.; Szumlak, T.; T'Jampens, S.; Teklishyn, M.; Tellarini, G.; Teodorescu, E.; Teubert, F.; Thomas, C.; Thomas, E.; Van Tilburg, J.; Tisserand, V.; Tobin, M. N.; Tolk, S.; Tomassetti, L.; Tonelli, D.; Topp-Joergensen, S.; Torr, N.; Tournefier, E.; Tourneur, S.; Tran, N.T.M.T.; Tresch, M.; Tsaregorodtsev, A.; Tsopelas, P.; Tuning, N.; Ubeda Garcia, M.; Ukleja, A.; Ustyuzhanin, A.; Uwer, U.; Vagnoni, V.; Valenti, G.; Vallier, A.; Vazquez Gomez, R.; Vazquez Regueiro, P.; Vázquez Sierra, C.; Vecchi, S.; Velthuis, M.J.; Veltri, M.; Veneziano, G.; Vesterinen, M.; Viaud, B.; Vieira, D.; Vilasis-Cardona, X.; Vollhardt, A.; Volyanskyy, D.; Voong, D.; Vorobyev, A.; Vorobyev, V.; Voß, C.; Voss, H.; De Vries, J. A.; Waldi, R.; Wallace, C.; Wallace, R.; Wandernoth, S.; Wang, J.; Ward, D. R.; Watson, N. K.; Webber, A. D.; Websdale, D.; Whitehead, M.; Wicht, J.; Wiechczynski, J.; Wiedner, D.; Wiggers, L.; Wilkinson, G.; Williams, M.P.; Williams, M.; Wilson, James F; Wimberley, J.; Wishahi, J.; Wislicki, W.; Witek, M.; Wormser, G.; Wotton, S. A.; Wright, S.J.; Wu, S.; Wyllie, K.; Xie, Y.; Xing, Z.; Yang, Z.; Yuan, X.; Yushchenko, O.; Zangoli, M.; Zavertyaev, M.; Zhang, F.; Zhang, L.; Zhang, W. C.; Zhang, Y.; Zhelezov, A.; Zhokhov, A.; Zhong, L.; Zvyagin, A.

    2014-01-01

    Decays of beauty baryons to the D0ph- and Λc+h- final states (where h indicates a pion or a kaon) are studied using a data sample of pp collisions, corresponding to an integrated luminosity of 1.0 fb-1, collected by the LHCb detector. The Cabibbo-suppressed decays Λb0→D0pK- and Λb0→Λc+K- are

  3. Cobalt dinitrosoalkane complexes in the C-H functionalization of olefins.

    Science.gov (United States)

    Schomaker, Jennifer M; Boyd, W Christopher; Stewart, Ian C; Toste, F Dean; Bergman, Robert G

    2008-03-26

    The use of cobalt dinitrosoalkane complexes in the C-H functionalization of alkenes has been demonstrated. Reaction of a series of alkenes with Me4CpCo(CO)2 in the presence of NO generates intermediate cobalt dinitrosoalkane complexes that can be deprotonated alpha to the nitrosyl group and added to various Michael acceptors. The resultant products can then undergo retrocycloaddition reactions in the presence of the original alkene to regenerate the starting cobalt dinitrosoalkane complex and release the functionalized alkene.

  4. Synthesis of Lycodine-Type Lycopodium Alkaloids Using C-H Functionalization Tactics

    OpenAIRE

    Newton, James

    2015-01-01

    This dissertation describes our syntheses of several lycodine-type Lycopodium alkaloids by the late-stage C-H functionalization of lycodine derivatives. Lycodine-type alkaloids are well-known for their neurological activity. For example, huperzine A is a potent acetylcholinesterase inhibitor and the complanadine family of molecules has been shown to induce the secretion of Nerve Growth Factor. Due to these properties, lycodine-type alkaloids serve as interesting lead compounds for the deve...

  5. Synthesis of all eight L-glycopyranosyl donors using C-H activation

    DEFF Research Database (Denmark)

    Frihed, Tobias; Pedersen, Christian Marcus; Bols, Mikael

    2014-01-01

    by an intramolecular C-H activation of the methyl group in g-position; both steps were catalyzed by iridium. The following Fleming-Tamao oxidation and acetylation gave the suitably protected L-hexoses. This is the first general method for the preparation of all eight L-hexoses as their thioglycosyl donors ready...... for glycosylation and the first example of an iridium-catalyzed C(sp3)-H activation on sulfide-containing compounds....

  6. Synthesis of oxindole from acetanilide via Ir(iii)-catalyzed C-H carbenoid functionalization.

    Science.gov (United States)

    Patel, Pitambar; Borah, Gongutri

    2016-12-22

    Herein we disclose the first report on the synthesis of oxindole derivatives from acetanilide via Ir(iii)-catalyzed intermolecular C-H functionalization with diazotized Meldrum's acid. A broad range of substituted anilides were found to react smoothly under the Ir(iii)-catalytic system to afford the corresponding N-protected oxindoles. The N-protecting groups, such as Ac, Bz or Piv, can be easily removed to furnish the oxindole. Various synthetic applications of the synthesized oxindole were also demonstrated.

  7. Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation.

    Science.gov (United States)

    Zheng, Yi-Wen; Chen, Bin; Ye, Pan; Feng, Ke; Wang, Wenguang; Meng, Qing-Yuan; Wu, Li-Zhu; Tung, Chen-Ho

    2016-08-17

    We present a blueprint for aromatic C-H functionalization via a combination of photocatalysis and cobalt catalysis and describe the utility of this strategy for benzene amination and hydroxylation. Without any sacrificial oxidant, we could use the dual catalyst system to produce aniline directly from benzene and ammonia, and phenol from benzene and water, both with evolution of hydrogen gas under unusually mild conditions in excellent yields and selectivities.

  8. Exploring Monte Carlo methods

    CERN Document Server

    Dunn, William L

    2012-01-01

    Exploring Monte Carlo Methods is a basic text that describes the numerical methods that have come to be known as "Monte Carlo." The book treats the subject generically through the first eight chapters and, thus, should be of use to anyone who wants to learn to use Monte Carlo. The next two chapters focus on applications in nuclear engineering, which are illustrative of uses in other fields. Five appendices are included, which provide useful information on probability distributions, general-purpose Monte Carlo codes for radiation transport, and other matters. The famous "Buffon's needle proble

  9. Monte Carlo methods

    Directory of Open Access Journals (Sweden)

    Bardenet Rémi

    2013-07-01

    Full Text Available Bayesian inference often requires integrating some function with respect to a posterior distribution. Monte Carlo methods are sampling algorithms that allow to compute these integrals numerically when they are not analytically tractable. We review here the basic principles and the most common Monte Carlo algorithms, among which rejection sampling, importance sampling and Monte Carlo Markov chain (MCMC methods. We give intuition on the theoretical justification of the algorithms as well as practical advice, trying to relate both. We discuss the application of Monte Carlo in experimental physics, and point to landmarks in the literature for the curious reader.

  10. Bonds Boom.

    Science.gov (United States)

    Reynolds, Cathryn

    1989-01-01

    The combined effect of the "Serrano" decision and Proposition 13 left California school districts with aging, overcrowded facilities. Chico schools won a $18.5 million general obligation bond election for facilities construction. With $11 billion needed for new school construction, California will need to tap local sources. A sidebar…

  11. Monte Carlo: Basics

    OpenAIRE

    Murthy, K. P. N.

    2001-01-01

    An introduction to the basics of Monte Carlo is given. The topics covered include, sample space, events, probabilities, random variables, mean, variance, covariance, characteristic function, chebyshev inequality, law of large numbers, central limit theorem (stable distribution, Levy distribution), random numbers (generation and testing), random sampling techniques (inversion, rejection, sampling from a Gaussian, Metropolis sampling), analogue Monte Carlo and Importance sampling (exponential b...

  12. The azomethine ylide route to amine C-H functionalization: redox-versions of classic reactions and a pathway to new transformations.

    Science.gov (United States)

    Seidel, Daniel

    2015-02-17

    Conspectus Redox-neutral methods for the functionalization of amine α-C-H bonds are inherently efficient because they avoid external oxidants and reductants and often do not generate unwanted byproducts. However, most of the current methods for amine α-C-H bond functionalization are oxidative in nature. While the most efficient variants utilize atmospheric oxygen as the terminal oxidant, many such transformations require the use of expensive or toxic oxidants, often coupled with the need for transition metal catalysts. Redox-neutral amine α-functionalizations that involve intramolecular hydride transfer steps provide viable alternatives to certain oxidative reactions. These processes have been known for some time and are particularly well suited for tertiary amine substrates. A mechanistically distinct strategy for secondary amines has emerged only recently, despite sharing common features with a range of classic organic transformations. Among those are such widely used reactions as the Strecker, Mannich, Pictet-Spengler, and Kabachnik-Fields reactions, Friedel-Crafts alkylations, and iminium alkynylations. In these classic processes, condensation of a secondary amine with an aldehyde (or a ketone) typically leads to the formation of an intermediate iminium ion, which is subsequently attacked by a nucleophile. The corresponding redox-versions of these transformations utilize identical starting materials but incorporate an isomerization step that enables α-C-H bond functionalization. Intramolecular versions of these reactions include redox-neutral amine α-amination, α-oxygenation, and α-sulfenylation. In all cases, a reductive N-alkylation is effectively combined with an oxidative α-functionalization, generating water as the only byproduct. Reactions are promoted by simple carboxylic acids and in some cases require no additives. Azomethine ylides, dipolar species whose usage is predominantly in [3 + 2] cycloadditions and other pericyclic processes, have been

  13. Diffusion bonding

    International Nuclear Information System (INIS)

    Anderson, R.C.

    1976-01-01

    A method is described for joining beryllium to beryllium by diffusion bonding. At least one surface portion of at least two beryllium pieces is coated with nickel. A coated surface portion is positioned in a contiguous relationship with another surface portion and subjected to an environment having an atmosphere at a pressure lower than ambient pressure. A force is applied on the beryllium pieces for causing the contiguous surface portions to abut against each other. The contiguous surface portions are heated to a maximum temperature less than the melting temperature of the beryllium, and the applied force is decreased while increasing the temperature after attaining a temperature substantially above room temperature. A portion of the applied force is maintained at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions

  14. Tribological properties of TiC/a-C:H nanocomposite coatings prepared via HiPIMS

    Science.gov (United States)

    Sánchez-López, J. C.; Dominguez-Meister, S.; Rojas, T. C.; Colasuonno, M.; Bazzan, M.; Patelli, A.

    2018-05-01

    High power impulse magnetron sputtering (HiPIMS) technology has been employed to prepare TiC/a-C:H nanocomposite coatings from a titanium target in acetylene (C2H2) reactive atmospheres. Gas fluxes were varied from 1.3 to 4.4 sccm to obtain C/Ti ratios from 2 to 15 as measured by electron probe microanalysis (EPMA). X-ray diffraction and transmission electron microscopy demonstrate the presence of TiC nanocrystals embedded in an amorphous carbon-based matrix. The hardness properties decrease from 17 to 10 GPa as the carbon content increases. The tribological properties were measured using a pin-on-disk tribometer in ambient air (RH = 30-40%) at 10 cm/s with 5 N of applied load against 6-mm 100Cr6 balls. The friction coefficient and the film wear rates are gradually improved from 0.3 and 7 × 10-6 mm3/N m to 0.15 and 2 × 10-7 mm3/N m, respectively, by increasing the C2H2 flux. To understand the tribological processes appearing at the interface and to elucidate the wear mechanism, microstructural and chemical investigations of the coatings were performed before and after the friction test. EPMA, X-ray photoelectron and electron energy-loss spectroscopies were employed to obtain an estimation of the fraction of the a-C:H phase, which can be correlated with the tribological behavior. Examination of the friction counterfaces (ball and track) by Raman microanalysis reveals an increased ordering of the amorphous carbon phase concomitant with friction reduction. The tribological results were compared with similar TiC/a-C(:H) composites prepared by the conventional direct current process.

  15. C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

    Science.gov (United States)

    Shul'pin, Georgiy B

    2013-09-28

    This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2

  16. Pd-Catalyzed C-H activation/oxidative cyclization of acetanilide with norbornene: concise access to functionalized indolines.

    Science.gov (United States)

    Gao, Yang; Huang, Yubing; Wu, Wanqing; Huang, Kefan; Jiang, Huanfeng

    2014-08-07

    An efficient Pd-catalyzed oxidative cyclization reaction for the synthesis of functionalized indolines by direct C-H activation of acetanilide has been developed. The norbornylpalladium species formed via direct ortho C-H activation of acetanilides is supposed to be a key intermediate in this transformation.

  17. Kinetics of Hydrocarbon formation in a- C:H Film deposition plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Cal, E de la; Tabares, F L

    1993-07-01

    The formation of C2 and Cp hydrocarbons during the PACVD of a-C:H films from admixtures of methane with H2 and He has been investigated by mass spectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanisms of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene formation was found to be directly related to the formation of the film on top of the carburized metal. (Author) 12 refs.

  18. Negative ion emission at field electron emission from amorphous (alpha-C:H) carbon

    CERN Document Server

    Bernatskij, D P; Ivanov-Omskij, V I; Pavlov, V G; Zvonareva, T K

    2001-01-01

    The study on the electrons field emission from the plane cathode surface on the basis of the amorphous carbon film (alpha-C:H) is carried out. The methodology, making it possible to accomplish simultaneously the registration of the emission currents and visually observe the distribution of the emission centers on the plane emitter surface is developed. The analysis of the oscillograms indicated that apart from the proper electron constituent the negative ions of hydrogen (H sup - and H sub 2 sup -), carbon (C sup -) and hydrocarbon (CH sub n sup -) are observed. The ions emission is connected with the processes of formation and degradation of the local emission centers

  19. Kinetics of Hydrocarbon formation in a-C:H film deposition plasmas

    International Nuclear Information System (INIS)

    De la Cal, E.; Tabares, F.L.

    1993-01-01

    The formation of C 2 and C 3 hydrocarbons during the PACVD of a-C-H films from admixtures of methane with H 2 and He has been investigated by mass spectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanism of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the carburized metal. (Author)

  20. Kinetics of Hydrocarbon formation in a-C:H Film deposition plasmas

    International Nuclear Information System (INIS)

    Cal, E. de la; Tabares, F. L.

    1993-01-01

    The formation of C2 and Cp hydrocarbons during the PACVD of a-C:H films from admixtures of methane with H2 and He has been investigated by mass spectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanisms of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene formation was found to be directly related to the formation of the film on top of the carburized metal. (Author) 12 refs

  1. Rhodium-catalyzed C-H alkynylation of arenes at room temperature.

    Science.gov (United States)

    Feng, Chao; Loh, Teck-Peng

    2014-03-03

    The rhodium(III)-catalyzed ortho C-H alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. C2-Selective Branched Alkylation of Benzimidazoles by Rhodium(I)-Catalyzed C-H Activation.

    Science.gov (United States)

    Tran, Gaël; Confair, Danielle; Hesp, Kevin D; Mascitti, Vincent; Ellman, Jonathan A

    2017-09-01

    Herein, we report a Rh(I)/bisphosphine/K 3 PO 4 catalytic system allowing for the first time the selective branched C-H alkylation of benzimidazoles with Michael acceptors. Branched alkylation with N,N-dimethyl acrylamide was successfully applied to the alkylation of a broad range of benzimidazoles incorporating a variety of N-substituents and with both electron-rich and -poor functionality displayed at different sites of the arene. Moreover, the introduction of a quaternary carbon was achieved by alkylation with ethyl methacrylate. The method was also shown to be applicable to the C2-selective branched alkylation of azabenzimidazoles.

  3. The Effect of Thermal Annealing on the Optical Properties of a-SiC:H Films Produced by DC Sputtering Methods: I

    Directory of Open Access Journals (Sweden)

    Lusitra Munisa

    2003-04-01

    Full Text Available Silicon Target Case. The effects of thermal annealing treatment on the optical properties of amorphous silicon carbon films deposited by silicon target in an argon, methane and hydrogen gas mixture have been studied using ultra violet-visible (uv-vis spectroscopy. Both n and α, and consequently the real and imaginary parts of the dielectric constant, show a considerable variation with subsequent annealing up to annealing temperature 500 °C, with the most rapid changes occurring for temperature 300 °C. The films tend denser as the annealing temperature increased up to 500°C. The optical gap improved slightly upon annealing, where as the disorder of the amorphous network reduced. The annealing treatment produces reorganization of the amorphous network since thermal annealing results in dissociation of hydrogenated bonds (Si-H and C-H.

  4. Composite Ag/C:H:N films prepared by planar magnetron deposition

    Energy Technology Data Exchange (ETDEWEB)

    Hlidek, P. [Charles University, Faculty of Mathematics and Physics, Praha (Czech Republic)], E-mail: hlidek@karlov.mff.cuni.cz; Hanus, J.; Biederman, H.; Slavinska, D.; Pesicka, J. [Charles University, Faculty of Mathematics and Physics, Praha (Czech Republic)

    2008-05-30

    Composite Ag/C:H:N films were deposited by means of an unbalanced magnetron operated in a gas mixture of nitrogen and n-hexane. Composition of the films was controlled by electric power delivered to the magnetron and by ratio of nitrogen and n-hexane in the working gas mixture. The films were characterized using transmission electron microscopy, by the absorption spectra in visible and near infrared regions and by Fourier transform infrared spectroscopy. Immediately after film deposition and without breaking vacuum (in situ) corresponding vibration infrared spectra were scanned and their evolution during ageing of the films was monitored. Wettability as determined from water contact angle was improved with raising nitrogen contents, i.e. with increasing the electric power and the ratio of nitrogen/n-hexane in the working gas mixture. The increased wettability is likely caused by presence of NH{sub x} groups in Ag/C:H:N films. The incorporation of nitrogen effectively prevents the formation of carboxylate groups on the silver inclusions surfaces during the aging in the open air. In addition, the oxidation mechanism of the polymer matrix is modified.

  5. Biocompatible Silver-containing a-C:H and a-C coatings: AComparative Study

    Energy Technology Data Exchange (ETDEWEB)

    Endrino, Jose Luis; Allen, Matthew; Escobar Galindo, Ramon; Zhang, Hanshen; Anders, Andre; Albella, Jose Maria

    2007-04-01

    Hydrogenated diamond-like-carbon (a-C:H) and hydrogen-free amorphous carbon (a-C) coatings are known to be biocompatible and have good chemical inertness. For this reason, both of these materials are strong candidates to be used as a matrix that embeds metallic elements with antimicrobial effect. In this comparative study, we have incorporated silver into diamond-like carbon (DLC) coatings by plasma based ion implantation and deposition (PBII&D) using methane (CH4) plasma and simultaneously depositing Ag from a pulsed cathodic arc source. In addition, we have grown amorphous carbon - silver composite coatings using a dual-cathode pulsed filtered cathodic-arc (FCA) source. The silver atomic content of the deposited samples was analyzed using glow discharge optical spectroscopy (GDOES). In both cases, the arc pulse frequency of the silver cathode was adjusted in order to obtain samples with approximately 5 at.% of Ag. Surface hardness of the deposited films was analyzed using the nanoindentation technique. Cell viability for both a-C:H/Ag and a-C:/Ag samples deposited on 24-well tissue culture plates has been evaluated.

  6. MORSE Monte Carlo code

    International Nuclear Information System (INIS)

    Cramer, S.N.

    1984-01-01

    The MORSE code is a large general-use multigroup Monte Carlo code system. Although no claims can be made regarding its superiority in either theoretical details or Monte Carlo techniques, MORSE has been, since its inception at ORNL in the late 1960s, the most widely used Monte Carlo radiation transport code. The principal reason for this popularity is that MORSE is relatively easy to use, independent of any installation or distribution center, and it can be easily customized to fit almost any specific need. Features of the MORSE code are described

  7. Variational Monte Carlo Technique

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 19; Issue 8. Variational Monte Carlo Technique: Ground State Energies of Quantum Mechanical Systems. Sukanta Deb. General Article Volume 19 Issue 8 August 2014 pp 713-739 ...

  8. Clean and Selective Catalytic C-H alkylation of Alkenes with Environmental friendly Alcohols

    KAUST Repository

    Poater, Albert

    2016-09-14

    Bearing the alkylation of alkene substrates using alcohol as solvent, catalysed by the cationic Ru-based catalyst [(C6H6)(PCy3)(CO)RuH]+, DFT calculations have been carried out to get mechanistic insights of such an environmental friendly reaction. Hard experimental conditions of Yi and coworkers [Science2011, 333, 1613] allow the formation of a C-C bond between indene and ethanol. The predicted mechanism suggests a cationic Ru-alkenyl species once two equivalents of indene interact releasing a molecule of indane subproduct. Then, oxidative addition of the Csingle bondO bond of alcohol to Ru-alkenyl species leads to Ru-alkenyl-alkyl species, followed by the reductive elimination process produces the desired alkylation product and a Ru-hydroxo complex. Finally, vinylic Csingle bondH activation and water elimination regenerates the Ru-alkenyl species. In this paper we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Furthermore, the present study explains the possible reasons for the absence of undesired products such as indene dimer or hydroxylated indene in the experiments.

  9. Studies of beauty baryon decays to $D^0 ph^-$ and $\\Lambda_c^+ h^-$ final states

    CERN Document Server

    Aaij, Roel; Adinolfi, Marco; Adrover, Cosme; Affolder, Anthony; Ajaltouni, Ziad; Albrecht, Johannes; Alessio, Federico; Alexander, Michael; Ali, Suvayu; Alkhazov, Georgy; Alvarez Cartelle, Paula; Alves Jr, Antonio; Amato, Sandra; Amerio, Silvia; Amhis, Yasmine; Anderlini, Lucio; Anderson, Jonathan; Andreassen, Rolf; Andreotti, Mirco; Andrews, Jason; Appleby, Robert; Aquines Gutierrez, Osvaldo; Archilli, Flavio; Artamonov, Alexander; Artuso, Marina; Aslanides, Elie; Auriemma, Giulio; Baalouch, Marouen; Bachmann, Sebastian; Back, John; Badalov, Alexey; Balagura, Vladislav; Baldini, Wander; Barlow, Roger; Barschel, Colin; Barsuk, Sergey; Barter, William; Batozskaya, Varvara; Bauer, Thomas; Bay, Aurelio; Beddow, John; Bedeschi, Franco; Bediaga, Ignacio; Belogurov, Sergey; Belous, Konstantin; Belyaev, Ivan; Ben-Haim, Eli; Bencivenni, Giovanni; Benson, Sean; Benton, Jack; Berezhnoy, Alexander; Bernet, Roland; Bettler, Marc-Olivier; van Beuzekom, Martinus; Bien, Alexander; Bifani, Simone; Bird, Thomas; Bizzeti, Andrea; Bjørnstad, Pål Marius; Blake, Thomas; Blanc, Frédéric; Blouw, Johan; Blusk, Steven; Bocci, Valerio; Bondar, Alexander; Bondar, Nikolay; Bonivento, Walter; Borghi, Silvia; Borgia, Alessandra; Bowcock, Themistocles; Bowen, Espen Eie; Bozzi, Concezio; Brambach, Tobias; van den Brand, Johannes; Bressieux, Joël; Brett, David; Britsch, Markward; Britton, Thomas; Brook, Nicholas; Brown, Henry; Bursche, Albert; Busetto, Giovanni; Buytaert, Jan; Cadeddu, Sandro; Calabrese, Roberto; Callot, Olivier; Calvi, Marta; Calvo Gomez, Miriam; Camboni, Alessandro; Campana, Pierluigi; Campora Perez, Daniel; Carbone, Angelo; Carboni, Giovanni; Cardinale, Roberta; Cardini, Alessandro; Carranza-Mejia, Hector; Carson, Laurence; Carvalho Akiba, Kazuyoshi; Casse, Gianluigi; Castillo Garcia, Lucia; Cattaneo, Marco; Cauet, Christophe; Cenci, Riccardo; Charles, Matthew; Charpentier, Philippe; Cheung, Shu-Faye; Chiapolini, Nicola; Chrzaszcz, Marcin; Ciba, Krzystof; Cid Vidal, Xabier; Ciezarek, Gregory; Clarke, Peter; Clemencic, Marco; Cliff, Harry; Closier, Joel; Coca, Cornelia; Coco, Victor; Cogan, Julien; Cogneras, Eric; Collins, Paula; Comerma-Montells, Albert; Contu, Andrea; Cook, Andrew; Coombes, Matthew; Coquereau, Samuel; Corti, Gloria; Couturier, Benjamin; Cowan, Greig; Craik, Daniel Charles; Cruz Torres, Melissa Maria; Cunliffe, Samuel; Currie, Robert; D'Ambrosio, Carmelo; Dalseno, Jeremy; David, Pascal; David, Pieter; Davis, Adam; De Bonis, Isabelle; De Bruyn, Kristof; De Capua, Stefano; De Cian, Michel; De Miranda, Jussara; De Paula, Leandro; De Silva, Weeraddana; De Simone, Patrizia; Decamp, Daniel; Deckenhoff, Mirko; Del Buono, Luigi; Déléage, Nicolas; Derkach, Denis; Deschamps, Olivier; Dettori, Francesco; Di Canto, Angelo; Dijkstra, Hans; Dogaru, Marius; Donleavy, Stephanie; Dordei, Francesca; Dorosz, Piotr; Dosil Suárez, Alvaro; Dossett, David; Dovbnya, Anatoliy; Dupertuis, Frederic; Durante, Paolo; Dzhelyadin, Rustem; Dziurda, Agnieszka; Dzyuba, Alexey; Easo, Sajan; Egede, Ulrik; Egorychev, Victor; Eidelman, Semen; van Eijk, Daan; Eisenhardt, Stephan; Eitschberger, Ulrich; Ekelhof, Robert; Eklund, Lars; El Rifai, Ibrahim; Elsasser, Christian; Falabella, Antonio; Färber, Christian; Farinelli, Chiara; Farry, Stephen; Ferguson, Dianne; Fernandez Albor, Victor; Ferreira Rodrigues, Fernando; Ferro-Luzzi, Massimiliano; Filippov, Sergey; Fiore, Marco; Fiorini, Massimiliano; Fitzpatrick, Conor; Fontana, Marianna; Fontanelli, Flavio; Forty, Roger; Francisco, Oscar; Frank, Markus; Frei, Christoph; Frosini, Maddalena; Furfaro, Emiliano; Gallas Torreira, Abraham; Galli, Domenico; Gandelman, Miriam; Gandini, Paolo; Gao, Yuanning; Garofoli, Justin; Garosi, Paola; Garra Tico, Jordi; Garrido, Lluis; Gaspar, Clara; Gauld, Rhorry; Gersabeck, Evelina; Gersabeck, Marco; Gershon, Timothy; Ghez, Philippe; Gibson, Valerie; Giubega, Lavinia-Helena; Gligorov, V.V.; Göbel, Carla; Golubkov, Dmitry; Golutvin, Andrey; Gomes, Alvaro; Gordon, Hamish; Grabalosa Gándara, Marc; Graciani Diaz, Ricardo; Granado Cardoso, Luis Alberto; Graugés, Eugeni; Graziani, Giacomo; Grecu, Alexandru; Greening, Edward; Gregson, Sam; Griffith, Peter; Grillo, Lucia; Grünberg, Oliver; Gui, Bin; Gushchin, Evgeny; Guz, Yury; Gys, Thierry; Hadjivasiliou, Christos; Haefeli, Guido; Haen, Christophe; Hafkenscheid, Tom; Haines, Susan; Hall, Samuel; Hamilton, Brian; Hampson, Thomas; Hansmann-Menzemer, Stephanie; Harnew, Neville; Harnew, Samuel; Harrison, Jonathan; Hartmann, Thomas; He, Jibo; Head, Timothy; Heijne, Veerle; Hennessy, Karol; Henrard, Pierre; Hernando Morata, Jose Angel; van Herwijnen, Eric; Heß, Miriam; Hicheur, Adlène; Hicks, Emma; Hill, Donal; Hoballah, Mostafa; Hombach, Christoph; Hulsbergen, Wouter; Hunt, Philip; Huse, Torkjell; Hussain, Nazim; Hutchcroft, David; Hynds, Daniel; Iakovenko, Viktor; Idzik, Marek; Ilten, Philip; Jacobsson, Richard; Jaeger, Andreas; Jans, Eddy; Jaton, Pierre; Jawahery, Abolhassan; Jing, Fanfan; John, Malcolm; Johnson, Daniel; Jones, Christopher; Joram, Christian; Jost, Beat; Jurik, Nathan; Kaballo, Michael; Kandybei, Sergii; Kanso, Wallaa; Karacson, Matthias; Karbach, Moritz; Kenyon, Ian; Ketel, Tjeerd; Khanji, Basem; Klaver, Suzanne; Kochebina, Olga; Komarov, Ilya; Koopman, Rose; Koppenburg, Patrick; Korolev, Mikhail; Kozlinskiy, Alexandr; Kravchuk, Leonid; Kreplin, Katharina; Kreps, Michal; Krocker, Georg; Krokovny, Pavel; Kruse, Florian; Kucharczyk, Marcin; Kudryavtsev, Vasily; Kurek, Krzysztof; Kvaratskheliya, Tengiz; La Thi, Viet Nga; Lacarrere, Daniel; Lafferty, George; Lai, Adriano; Lambert, Dean; Lambert, Robert W; Lanciotti, Elisa; Lanfranchi, Gaia; Langenbruch, Christoph; Latham, Thomas; Lazzeroni, Cristina; Le Gac, Renaud; van Leerdam, Jeroen; Lees, Jean-Pierre; Lefèvre, Regis; Leflat, Alexander; Lefrançois, Jacques; Leo, Sabato; Leroy, Olivier; Lesiak, Tadeusz; Leverington, Blake; Li, Yiming; Li Gioi, Luigi; Liles, Myfanwy; Lindner, Rolf; Linn, Christian; Lionetto, Federica; Liu, Bo; Liu, Guoming; Lohn, Stefan; Longstaff, Ian; Lopes, Jose; Lopez-March, Neus; Lu, Haiting; Lucchesi, Donatella; Luisier, Johan; Luo, Haofei; Luppi, Eleonora; Lupton, Oliver; Machefert, Frederic; Machikhiliyan, Irina V; Maciuc, Florin; Maev, Oleg; Malde, Sneha; Manca, Giulia; Mancinelli, Giampiero; Maratas, Jan; Marconi, Umberto; Marino, Pietro; Märki, Raphael; Marks, Jörg; Martellotti, Giuseppe; Martens, Aurelien; Martín Sánchez, Alexandra; Martinelli, Maurizio; Martinez Santos, Diego; Martins Tostes, Danielle; Martynov, Aleksandr; Massafferri, André; Matev, Rosen; Mathe, Zoltan; Matteuzzi, Clara; Maurice, Emilie; Mazurov, Alexander; McCann, Michael; McCarthy, James; McNab, Andrew; McNulty, Ronan; McSkelly, Ben; Meadows, Brian; Meier, Frank; Meissner, Marco; Merk, Marcel; Milanes, Diego Alejandro; Minard, Marie-Noelle; Molina Rodriguez, Josue; Monteil, Stephane; Moran, Dermot; Morawski, Piotr; Mordà, Alessandro; Morello, Michael Joseph; Mountain, Raymond; Mous, Ivan; Muheim, Franz; Müller, Katharina; Muresan, Raluca; Muryn, Bogdan; Muster, Bastien; Naik, Paras; Nakada, Tatsuya; Nandakumar, Raja; Nasteva, Irina; Needham, Matthew; Neubert, Sebastian; Neufeld, Niko; Nguyen, Anh Duc; Nguyen, Thi-Dung; Nguyen-Mau, Chung; Nicol, Michelle; Niess, Valentin; Niet, Ramon; Nikitin, Nikolay; Nikodem, Thomas; Nomerotski, Andrey; Novoselov, Alexey; Oblakowska-Mucha, Agnieszka; Obraztsov, Vladimir; Oggero, Serena; Ogilvy, Stephen; Okhrimenko, Oleksandr; Oldeman, Rudolf; Onderwater, Gerco; Orlandea, Marius; Otalora Goicochea, Juan Martin; Owen, Patrick; Oyanguren, Maria Arantza; Pal, Bilas Kanti; Palano, Antimo; Palutan, Matteo; Panman, Jacob; Papanestis, Antonios; Pappagallo, Marco; Pappalardo, Luciano; Parkes, Christopher; Parkinson, Christopher John; Passaleva, Giovanni; Patel, Girish; Patel, Mitesh; Patrignani, Claudia; Pavel-Nicorescu, Carmen; Pazos Alvarez, Antonio; Pearce, Alex; Pellegrino, Antonio; Penso, Gianni; Pepe Altarelli, Monica; Perazzini, Stefano; Perez Trigo, Eliseo; Pérez-Calero Yzquierdo, Antonio; Perret, Pascal; Perrin-Terrin, Mathieu; Pescatore, Luca; Pesen, Erhan; Pessina, Gianluigi; Petridis, Konstantin; Petrolini, Alessandro; Picatoste Olloqui, Eduardo; Pietrzyk, Boleslaw; Pilař, Tomas; Pinci, Davide; Playfer, Stephen; Plo Casasus, Maximo; Polci, Francesco; Polok, Grzegorz; Poluektov, Anton; Polycarpo, Erica; Popov, Alexander; Popov, Dmitry; Popovici, Bogdan; Potterat, Cédric; Powell, Andrew; Prisciandaro, Jessica; Pritchard, Adrian; Prouve, Claire; Pugatch, Valery; Puig Navarro, Albert; Punzi, Giovanni; Qian, Wenbin; Rachwal, Bartolomiej; Rademacker, Jonas; Rakotomiaramanana, Barinjaka; Rangel, Murilo; Raniuk, Iurii; Rauschmayr, Nathalie; Raven, Gerhard; Redford, Sophie; Reichert, Stefanie; Reid, Matthew; dos Reis, Alberto; Ricciardi, Stefania; Richards, Alexander; Rinnert, Kurt; Rives Molina, Vincente; Roa Romero, Diego; Robbe, Patrick; Roberts, Douglas; Rodrigues, Ana Barbara; Rodrigues, Eduardo; Rodriguez Perez, Pablo; Roiser, Stefan; Romanovsky, Vladimir; Romero Vidal, Antonio; Rotondo, Marcello; Rouvinet, Julien; Ruf, Thomas; Ruffini, Fabrizio; Ruiz, Hugo; Ruiz Valls, Pablo; Sabatino, Giovanni; Saborido Silva, Juan Jose; Sagidova, Naylya; Sail, Paul; Saitta, Biagio; Salustino Guimaraes, Valdir; Sanmartin Sedes, Brais; Santacesaria, Roberta; Santamarina Rios, Cibran; Santovetti, Emanuele; Sapunov, Matvey; Sarti, Alessio; Satriano, Celestina; Satta, Alessia; Savrie, Mauro; Savrina, Darya; Schiller, Manuel; Schindler, Heinrich; Schlupp, Maximilian; Schmelling, Michael; Schmidt, Burkhard; Schneider, Olivier; Schopper, Andreas; Schune, Marie Helene; Schwemmer, Rainer; Sciascia, Barbara; Sciubba, Adalberto; Seco, Marcos; Semennikov, Alexander; Senderowska, Katarzyna; Sepp, Indrek; Serra, Nicola; Serrano, Justine; Seyfert, Paul; Shapkin, Mikhail; Shapoval, Illya; Shcheglov, Yury; Shears, Tara; Shekhtman, Lev; Shevchenko, Oksana; Shevchenko, Vladimir; Shires, Alexander; Silva Coutinho, Rafael; Sirendi, Marek; Skidmore, Nicola; Skwarnicki, Tomasz; Smith, Anthony; Smith, Edmund; Smith, Eluned; Smith, Jackson; Smith, Mark; Sokoloff, Michael; Soler, Paul; Soomro, Fatima; Souza, Daniel; Souza De Paula, Bruno; Spaan, Bernhard; Sparkes, Ailsa; Spradlin, Patrick; Stagni, Federico; Stahl, Sascha; Steinkamp, Olaf; Stevenson, Scott; Stoica, Sabin; Stone, Sheldon; Storaci, Barbara; Stracka, Simone; Straticiuc, Mihai; Straumann, Ulrich; Subbiah, Vijay Kartik; Sun, Liang; Sutcliffe, William; Swientek, Stefan; Syropoulos, Vasileios; Szczekowski, Marek; Szczypka, Paul; Szilard, Daniela; Szumlak, Tomasz; T'Jampens, Stephane; Teklishyn, Maksym; Tellarini, Giulia; Teodorescu, Eliza; Teubert, Frederic; Thomas, Christopher; Thomas, Eric; van Tilburg, Jeroen; Tisserand, Vincent; Tobin, Mark; Tolk, Siim; Tomassetti, Luca; Tonelli, Diego; Topp-Joergensen, Stig; Torr, Nicholas; Tournefier, Edwige; Tourneur, Stephane; Tran, Minh Tâm; Tresch, Marco; Tsaregorodtsev, Andrei; Tsopelas, Panagiotis; Tuning, Niels; Ubeda Garcia, Mario; Ukleja, Artur; Ustyuzhanin, Andrey; Uwer, Ulrich; Vagnoni, Vincenzo; Valenti, Giovanni; Vallier, Alexis; Vazquez Gomez, Ricardo; Vazquez Regueiro, Pablo; Vázquez Sierra, Carlos; Vecchi, Stefania; Velthuis, Jaap; Veltri, Michele; Veneziano, Giovanni; Vesterinen, Mika; Viaud, Benoit; Vieira, Daniel; Vilasis-Cardona, Xavier; Vollhardt, Achim; Volyanskyy, Dmytro; Voong, David; Vorobyev, Alexey; Vorobyev, Vitaly; Voß, Christian; Voss, Helge; de Vries, Jacco; Waldi, Roland; Wallace, Charlotte; Wallace, Ronan; Wandernoth, Sebastian; Wang, Jianchun; Ward, David; Watson, Nigel; Webber, Adam Dane; Websdale, David; Whitehead, Mark; Wicht, Jean; Wiechczynski, Jaroslaw; Wiedner, Dirk; Wiggers, Leo; Wilkinson, Guy; Williams, Matthew; Williams, Mike; Wilson, Fergus; Wimberley, Jack; Wishahi, Julian; Wislicki, Wojciech; Witek, Mariusz; Wormser, Guy; Wotton, Stephen; Wright, Simon; Wu, Suzhi; Wyllie, Kenneth; Xie, Yuehong; Xing, Zhou; Yang, Zhenwei; Yuan, Xuhao; Yushchenko, Oleg; Zangoli, Maria; Zavertyaev, Mikhail; Zhang, Feng; Zhang, Liming; Zhang, Wen Chao; Zhang, Yanxi; Zhelezov, Alexey; Zhokhov, Anatoly; Zhong, Liang; Zvyagin, Alexander

    2014-01-01

    Decays of beauty baryons to the $D^0 p h^-$ and $\\Lambda_c^+ h^-$ final states (where $h$ indicates a pion or a kaon) are studied using a data sample of $pp$ collisions, corresponding to an integrated luminosity of 1.0 fb$^{-1}$, collected by the LHCb detector. The Cabibbo-suppressed decays $\\Lambda_b^0\\to D^0 p K^-$ and $\\Lambda_b^0\\to \\Lambda_c^+ K^-$ are observed and their branching fractions are measured with respect to the decays $\\Lambda_b^0\\to D^0 p \\pi^-$ and $\\Lambda_b^0\\to \\Lambda_c^+ \\pi^-$. In addition, the first observation is reported of the decay of the neutral beauty-strange baryon $\\Xi_b^0$ to the $D^0 p K^-$ final state, and a measurement of the $\\Xi_b^0$ mass is performed. Evidence of the $\\Xi_b^0\\to \\Lambda_c^+ K^-$ decay is also reported.

  10. R.E.A.C.H. to Teach: Making Patient and Family Education "Stick".

    Science.gov (United States)

    Cutilli, Carolyn Crane

    2016-01-01

    Healthcare professionals teach patients and families about their health every day. Regulatory and accreditation organizations mandate patient and family education to promote better health outcomes. And recently, financial rewards for healthcare organizations are being tied to patient satisfaction (Hospital Consumer Assessment of Healthcare Providers and Systems-HCAHPS). A University of Pennsylvania Health System group of staff and patients, devoted to excellence in patient and family education, developed the graphic "R.E.A.C.H. to Teach." The purpose of the graphic is to make evidence-based practice (EBP) for patient and family education "stick" with staff. The group used concepts from the marketing book, Made to Stick, to demonstrate how to develop effective staff and patient and family education. Ideas (education) that survive ("stick") have the following attributes: simple, unexpected, concrete, credible, emotional, and narrative (story). This article demonstrates how to apply these principles and EBP to patient and family education.

  11. The role of the excited electronic states in the C++H2O reaction

    International Nuclear Information System (INIS)

    Flores, Jesus R.; Gonzalez, Adan B.

    2008-01-01

    The electronic excited states of the [COH 2 ] + system have been studied in order to establish their role in the dynamics of the C + +H 2 O→[COH] + +H reaction, which is a prototypical ion-molecule reaction. The most relevant minima and saddle points of the lowest excited state have been determined and energy profiles for the lowest excited doublet and quartet electronic states have been computed along the fragmentation and isomerization coordinates. Also, nonadiabatic coupling strengths between the ground and the first excited state have been computed where they can be large. Our analysis suggests that the first excited state could play an important role in the generation of the formyl isomer, which has been detected in crossed beam experiments [D. M. Sonnenfroh et al., J. Chem. Phys. 83, 3985 (1985)], but could not be explained in quasiclassical trajectory computations [Y. Ishikawa et al., Chem. Phys. Lett. 370, 490 (2003); J. R. Flores, J. Chem. Phys. 125, 164309 (2006)

  12. Dual Ligand-Enabled Nondirected C-H Olefination of Arenes.

    Science.gov (United States)

    Chen, Hao; Wedi, Philipp; Meyer, Tim; Tavakoli, Ghazal; van Gemmeren, Manuel

    2018-02-23

    The application of the Pd-catalyzed oxidative C-H olefination of arenes, also known as the Fujiwara-Moritani reaction, has traditionally been limited by the requirement for directing groups on the substrate or the need to use the arene in large excess, typically as a (co)solvent. Herein the development of a catalytic system is described that, through the combined action of two complementary ligands, makes it possible to use directing-group-free arenes as limiting reagents for the first time. The reactions proceed under a combination of both steric and electronic control and enable the application of this powerful reaction to valuable arenes, which cannot be utilized in excess. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Substrate-Triggered Formation and Remarkable Stability of the C-H-Cleaving Chloroferryl Intermediate in the Aliphatic Halogenase, SyrB2†

    Science.gov (United States)

    Matthews, Megan L.; Krest, Courtney M.; Barr, Eric W.; Vaillancourt, Frédéric H.; Walsh, Christopher T.; Green, Michael T.; Krebs, Carsten; Bollinger, J. Martin

    2009-01-01

    Aliphatic halogenases activate O2, cleave α-ketoglutarate (αKG) to CO2 and succinate, and form haloferryl [X-Fe(IV)=O; X = Cl, Br] complexes that cleave aliphatic C-H bonds to install halogens during the biosynthesis of natural products by non-ribosomal peptide synthetases (NRPSs). For the related αKG-dependent dioxygenases, it has been shown that reaction of the Fe(II) cofactor with O2 to form the C-H-cleaving ferryl complex is “triggered” by binding of the target substrate. In this study, we have tested for and defined structural determinants of substrate triggering (ST) in the halogenase, SyrB2, from the syringomycin E biosynthetic NRPS of Pseudomonas syringae B301D. As for other halogen ases, the substrate of SyrB2 is complex, consisting of l-Thr tethered via thioester linkage to a covalently bound phosphopantetheine (PPant) cofactor of a carrier protein, SyrB1. Without an appended amino acid, SyrB1 does not trigger formation of the chloroferryl intermediate state in SyrB2, even in the presence of free l-Thr or its analogues, but SyrB1 charged either by l-Thr or by any of several non-native amino acids does trigger the reaction by as much as 8,000-fold (for l-Thr-S-SyrB1). Triggering efficacy is sensitive to the structures of both the amino acid and the carrier protein, being diminished by 5–20-fold when the native l-Thr is replaced by another amino acid and by ∼ 40-fold when SyrB1 is replaced by a heterologous carrier protein, CytC2. The directing effect of the carrier protein and consequent tolerance for profound modifications to the target amino acid allow the chloroferryl state to be formed in the presence of substrates that perturb the ratio of its two putative coordination isomers, lack the target C-H bond (l-Ala-S-SyrB1), or contain a C-H bond of enhanced strength (l-cyclopropylglycyl-S-SyrB1). For the latter two cases, the SyrB2 chloroferryl state so formed exhibits unprecedented stability (t1/2 = 30 – 110 min at 0 °C), can be trapped in

  14. Direct Aldehyde C-H Arylation and Alkylation via the Combination of Nickel, Hydrogen Atom Transfer, and Photoredox Catalysis.

    Science.gov (United States)

    Zhang, Xiaheng; MacMillan, David W C

    2017-08-23

    A mechanism that enables direct aldehyde C-H functionalization has been achieved via the synergistic merger of photoredox, nickel, and hydrogen atom transfer catalysis. This mild, operationally simple protocol transforms a wide variety of commercially available aldehydes, along with aryl or alkyl bromides, into the corresponding ketones in excellent yield. This C-H abstraction coupling technology has been successfully applied to the expedient synthesis of the medicinal agent haloperidol.

  15. Monte Carlo codes and Monte Carlo simulator program

    International Nuclear Information System (INIS)

    Higuchi, Kenji; Asai, Kiyoshi; Suganuma, Masayuki.

    1990-03-01

    Four typical Monte Carlo codes KENO-IV, MORSE, MCNP and VIM have been vectorized on VP-100 at Computing Center, JAERI. The problems in vector processing of Monte Carlo codes on vector processors have become clear through the work. As the result, it is recognized that these are difficulties to obtain good performance in vector processing of Monte Carlo codes. A Monte Carlo computing machine, which processes the Monte Carlo codes with high performances is being developed at our Computing Center since 1987. The concept of Monte Carlo computing machine and its performance have been investigated and estimated by using a software simulator. In this report the problems in vectorization of Monte Carlo codes, Monte Carlo pipelines proposed to mitigate these difficulties and the results of the performance estimation of the Monte Carlo computing machine by the simulator are described. (author)

  16. Vectorized Monte Carlo

    International Nuclear Information System (INIS)

    Brown, F.B.

    1981-01-01

    Examination of the global algorithms and local kernels of conventional general-purpose Monte Carlo codes shows that multigroup Monte Carlo methods have sufficient structure to permit efficient vectorization. A structured multigroup Monte Carlo algorithm for vector computers is developed in which many particle events are treated at once on a cell-by-cell basis. Vectorization of kernels for tracking and variance reduction is described, and a new method for discrete sampling is developed to facilitate the vectorization of collision analysis. To demonstrate the potential of the new method, a vectorized Monte Carlo code for multigroup radiation transport analysis was developed. This code incorporates many features of conventional general-purpose production codes, including general geometry, splitting and Russian roulette, survival biasing, variance estimation via batching, a number of cutoffs, and generalized tallies of collision, tracklength, and surface crossing estimators with response functions. Predictions of vectorized performance characteristics for the CYBER-205 were made using emulated coding and a dynamic model of vector instruction timing. Computation rates were examined for a variety of test problems to determine sensitivities to batch size and vector lengths. Significant speedups are predicted for even a few hundred particles per batch, and asymptotic speedups by about 40 over equivalent Amdahl 470V/8 scalar codes arepredicted for a few thousand particles per batch. The principal conclusion is that vectorization of a general-purpose multigroup Monte Carlo code is well worth the significant effort required for stylized coding and major algorithmic changes

  17. CERN honours Carlo Rubbia

    CERN Document Server

    2009-01-01

    Carlo Rubbia turned 75 on March 31, and CERN held a symposium to mark his birthday and pay tribute to his impressive contribution to both CERN and science. Carlo Rubbia, 4th from right, together with the speakers at the symposium.On 7 April CERN hosted a celebration marking Carlo Rubbia’s 75th birthday and 25 years since he was awarded the Nobel Prize for Physics. "Today we will celebrate 100 years of Carlo Rubbia" joked CERN’s Director-General, Rolf Heuer in his opening speech, "75 years of his age and 25 years of the Nobel Prize." Rubbia received the Nobel Prize along with Simon van der Meer for contributions to the discovery of the W and Z bosons, carriers of the weak interaction. During the symposium, which was held in the Main Auditorium, several eminent speakers gave lectures on areas of science to which Carlo Rubbia made decisive contributions. Among those who spoke were Michel Spiro, Director of the French National Insti...

  18. Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes.

    Science.gov (United States)

    Mei, Ruhuai; Sauermann, Nicolas; Oliveira, João C A; Ackermann, Lutz

    2018-06-27

    Electrochemical oxidative C-H/N-H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C-H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C-H activation catalysis, generating H 2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C-H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C-H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C-H/N-H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.

  19. Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis.

    Science.gov (United States)

    Twilton, Jack; Christensen, Melodie; DiRocco, Daniel A; Ruck, Rebecca T; Davies, Ian W; MacMillan, David W C

    2018-05-04

    The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α-hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate α-hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as α-amino and α-oxy C-H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Valuing Catastrophe Bonds Involving Credit Risks

    Directory of Open Access Journals (Sweden)

    Jian Liu

    2014-01-01

    Full Text Available Catastrophe bonds are the most important products in catastrophe risk securitization market. For the operating mechanism, CAT bonds may have a credit risk, so in this paper we consider the influence of the credit risk on CAT bonds pricing that is different from the other literature. We employ the Jarrow and Turnbull method to model the credit risks and get access to the general pricing formula using the Extreme Value Theory. Furthermore, we present an empirical pricing study of the Property Claim Services data, where the parameters in the loss function distribution are estimated by the MLE method and the default probabilities are deduced by the US financial market data. Then we get the catastrophe bonds value by the Monte Carlo method.

  1. Copper-promoted methylene C-H oxidation to a ketone derivative by O2.

    Science.gov (United States)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J

    2017-01-17

    The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O 2 in air under ambient conditions when [Cu(dpeo) 2 ](ClO 4 ) 2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO 4 ). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca - ), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca - are not recovered and [Cu(pic) 2 H 2 O] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O 2 activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by H 2 O 2 in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O 2 . The metastable copper complexes [Cu(dpeo) 2 ](ClO 4 ) 2 and [Cu(bpca)(hidpe)](ClO 4 ), along with [NiX 2 (dpeo) 2 ] (X = Cl, Br), [Ni(dpeo) 3 ](ClO 4 ) 2 , [Co(dpeo) 3 ](ClO 4 ) 3 and the mixed valence complex [Fe III Fe(dpeo-H) 3 (dpeo) 3 ](PF 6 ) 4 , have been structurally characterized.

  2. Bond strength of masonry

    NARCIS (Netherlands)

    Pluijm, van der R.; Vermeltfoort, A.Th.

    1992-01-01

    Bond strength is not a well defined property of masonry. Normally three types of bond strength can be distinguished: - tensile bond strength, - shear (and torsional) bond strength, - flexural bond strength. In this contribution the behaviour and strength of masonry in deformation controlled uniaxial

  3. Pricing Chinese Convertible Bonds with Dynamic Credit Risk

    Directory of Open Access Journals (Sweden)

    Ping Li

    2014-01-01

    Full Text Available To price convertible bonds more precisely, least squares Monte Carlo (LSM method is used in this paper for its advantage in handling the dependence of derivatives on the path, and dynamic credit risk is used to replace the fixed one to make the value of convertible bonds reflect the real credit risk. In the empirical study, we price convertible bonds based on static credit risk and dynamic credit risk, respectively. Empirical results indicate that the ICBC convertible bond has been overpriced, resulting from the underestimation of credit risk. In addition, when there is an issue of dividend, the conversion price will change in China's convertible bonds, while it does not change in the international convertible bonds. So we also empirically study the difference between the convertible bond's prices by assuming whether the conversion price changes or not.

  4. Mechanistic Insight into Ketone α-Alkylation with Unactivated Olefins via C-H Activation Promoted by Metal-Organic Cooperative Catalysis (MOCC): Enriching the MOCC Chemistry.

    Science.gov (United States)

    Dang, Yanfeng; Qu, Shuanglin; Tao, Yuan; Deng, Xi; Wang, Zhi-Xiang

    2015-05-20

    Metal-organic cooperative catalysis (MOCC) has been successfully applied for hydroacylation of olefins with aldehydes via directed C(sp(2))-H functionalization. Most recently, it was reported that an elaborated MOCC system, containing Rh(I) catalyst and 7-azaindoline (L1) cocatalyst, could even catalyze ketone α-alkylation with unactivated olefins via C(sp(3))-H activation. Herein we present a density functional theory study to understand the mechanism of the challenging ketone α-alkylation. The transformation uses IMesRh(I)Cl(L1)(CH2═CH2) as an active catalyst and proceeds via sequential seven steps, including ketone condensation with L1, giving enamine 1b; 1b coordination to Rh(I) active catalyst, generating Rh(I)-1b intermediate; C(sp(2))-H oxidative addition, leading to a Rh(III)-H hydride; olefin migratory insertion into Rh(III)-H bond; reductive elimination, generating Rh(I)-1c(alkylated 1b) intermediate; decoordination of 1c, liberating 1c and regenerating Rh(I) active catalyst; and hydrolysis of 1c, furnishing the final α-alkylation product 1d and regenerating L1. Among the seven steps, reductive elimination is the rate-determining step. The C-H bond preactivation via agostic interaction is crucial for the bond activation. The mechanism rationalizes the experimental puzzles: why only L1 among several candidates performed perfectly, whereas others failed, and why Wilkinson's catalyst commonly used in MOCC systems performed poorly. Based on the established mechanism and stimulated by other relevant experimental reactions, we attempted to enrich MOCC chemistry computationally, exemplifying how to develop new organic catalysts and proposing L7 to be an alternative for L1 and demonstrating the great potential of expanding the hitherto exclusive use of Rh(I)/Rh(III) manifold to Co(0)/Co(II) redox cycling in developing MOCC systems.

  5. Influence of modulation periods on the tribological behavior of Si/a-C: H multilayer film

    Science.gov (United States)

    Zhu, Linan; Wu, Yanxia; Zhang, Shujiao; Yu, Shengwang; Tang, Bin; Liu, Ying; Zhou, Bing; Shen, Yanyan

    2018-01-01

    A series of Si/a-C: H multilayer films with different modulation periods were fabricated on stainless steel and silicon substrates by radio-frequency magnetron sputtering. The influence of the modulation period on the structure, morphology, mechanical properties and tribological behaviors in different environments (air, simulated acid rain, and NaCl solution) was investigated. The results show that the content of the sp2 hybrid carbon, surface roughness and hardness of the multilayer film increased firstly and then decreased with the decreased modulation period. Furthermore, the combination of the sublayer agrees well with the formation of the SiC crystal at the interface. Interestingly, the films show quite substantially different tribological properties in various test environments. The lowest friction coefficient is 0.2 for the S1 film in air. However, the lowest friction coefficient can reach 0.13 in solution. Importantly, the tribological behavior of the multilayer film is mainly determined by its hardness, as well as surface roughness in air while it is closely related with modulation period and interface structure in solution.

  6. Adsorption of alcohols and fatty acids onto hydrogenated (a-C:H) DLC coatings

    Science.gov (United States)

    Simič, R.; Kalin, M.; Kovač, J.; Jakša, G.

    2016-02-01

    Information about the interactions between lubricants and DLC coatings is scarce, despite there having been many studies over the years. In this investigation we used ToF-SIMS, XPS and contact-angle analyses to examine the adsorption ability and mechanisms with respect to two oiliness additives, i.e., hexadecanol and hexadecanoic acid, on an a-C:H coating. In addition, we analyzed the resistance of the adsorbed films to external influences like solvent cleaning. The results show that both molecules adsorb onto surface oxides and hydroxides present on the initial DLC surface and shield these structures with their hydrocarbon tails. This makes the surfaces less polar, which is manifested in a smaller polar component of the surface energy. We also showed that ultrasonic cleaning in heptane has no significant effect on the quantity of adsorbed molecules or on their chemical state. This not only shows the relatively strong adsorption of these molecules, but also provides useful information for future experimental work. Of the two examined molecules, the acid showed a greater adsorption ability than the alcohol, which explains some of the previously reported better tribological properties in the case of the acid with respect to the alcohol.

  7. Carlo Caso (1940 - 2007)

    CERN Multimedia

    Leonardo Rossi

    Carlo Caso (1940 - 2007) Our friend and colleague Carlo Caso passed away on July 7th, after several months of courageous fight against cancer. Carlo spent most of his scientific career at CERN, taking an active part in the experimental programme of the laboratory. His long and fruitful involvement in particle physics started in the sixties, in the Genoa group led by G. Tomasini. He then made several experiments using the CERN liquid hydrogen bubble chambers -first the 2000HBC and later BEBC- to study various facets of the production and decay of meson and baryon resonances. He later made his own group and joined the NA27 Collaboration to exploit the EHS Spectrometer with a rapid cycling bubble chamber as vertex detector. Amongst their many achievements, they were the first to measure, with excellent precision, the lifetime of the charmed D mesons. At the start of the LEP era, Carlo and his group moved to the DELPHI experiment, participating in the construction and running of the HPC electromagnetic c...

  8. Variational Monte Carlo Technique

    Indian Academy of Sciences (India)

    ias

    on the development of nuclear weapons in Los Alamos ..... cantly improved the paper. ... Carlo simulations of solids, Reviews of Modern Physics, Vol.73, pp.33– ... The computer algorithms are usually based on a random seed that starts the ...

  9. Markov Chain Monte Carlo

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 7; Issue 3. Markov Chain Monte Carlo - Examples. Arnab Chakraborty. General Article Volume 7 Issue 3 March 2002 pp 25-34. Fulltext. Click here to view fulltext PDF. Permanent link: https://www.ias.ac.in/article/fulltext/reso/007/03/0025-0034. Keywords.

  10. Monte Carlo and Quasi-Monte Carlo Sampling

    CERN Document Server

    Lemieux, Christiane

    2009-01-01

    Presents essential tools for using quasi-Monte Carlo sampling in practice. This book focuses on issues related to Monte Carlo methods - uniform and non-uniform random number generation, variance reduction techniques. It covers several aspects of quasi-Monte Carlo methods.

  11. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    Undervisningsmateriale. A bond is a debt security, similar to an ”I Owe You document” (IOU). When you purchase a bond, you are lending money to a government, municipality, corporation, federal agency or other entity known as the issuer. In return for the loan, the issuer promises to pay you...... a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...... securities and foreign government bonds....

  12. Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes

    Science.gov (United States)

    Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz

    2017-06-01

    The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

  13. Human serum albumin (HSA) adsorption onto a-SiC:H thin films deposited by hot wire chemical vapor deposition

    International Nuclear Information System (INIS)

    Swain, Bibhu P.

    2006-01-01

    In the present paper, we report the study of the adsorption behavior of human serum albumin (HSA) onto surfaces of a-SiC:H thin films deposited by using the hot wire chemical vapor deposition (HWCVD) technique. The surface composition and surface energy of the various substrates as well as the evaluation of the adsorbed amount of protein has been carried out by means of X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) spectroscopy, AFM and contact angle measurements. At the immediate effect of HSA interaction with a-SiC:H films N is adsorbed on the surface and stabilized after 3 days. Preliminary observation found that Si and O atom are desorbed from the surface while C and N set adsorbed to the surface of the a-SiC:H film

  14. Human serum albumin (HSA) adsorption onto a-SiC:H thin films deposited by hot wire chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Swain, Bibhu P. [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology, Bombay (India) and Samtel Centre for Display Technologies, Indian Institute of Technology Kanpur, India, Kanpur 208016 (India)]. E-mail: bibhup@iitb.ac.in

    2006-12-15

    In the present paper, we report the study of the adsorption behavior of human serum albumin (HSA) onto surfaces of a-SiC:H thin films deposited by using the hot wire chemical vapor deposition (HWCVD) technique. The surface composition and surface energy of the various substrates as well as the evaluation of the adsorbed amount of protein has been carried out by means of X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) spectroscopy, AFM and contact angle measurements. At the immediate effect of HSA interaction with a-SiC:H films N is adsorbed on the surface and stabilized after 3 days. Preliminary observation found that Si and O atom are desorbed from the surface while C and N set adsorbed to the surface of the a-SiC:H film.

  15. Structural and mechanical properties of nc-TiC/a-C:H nanocomposite film prepared by dual plasma technique

    International Nuclear Information System (INIS)

    Wang Yaohui; Zhang Xu; Wu Xianying; Li Qiang; Zhang Huixing; Zhang Xiaoji

    2008-01-01

    Nanocomposite nc-TiC/a-C:H film, with an unusual combination of superhardness, high elastic modulus and high elastic recovery, are prepared by using the dual plasma technique. The effects of the filter coil current on the compositional, structural and mechanical properties of the nc-TiC/a-C:H films have been investigated. X-ray photoelectron spectroscopy (XPS) and Raman analyses show that deposition rate, composition and nanostructure of the nc-TiC/a-C:H films could be changed by varying the filter coil current. Fortunately, by selecting the proper value for the filter coil current, 2.5 A, one could remarkably enhance mechanical properties of films such as the superhardness (66.4 GPa), the high elastic modulus (510 GPa) and the high elastic recovery (83.3%)

  16. Hydrogen bonded C-H···Y (Y = O, S, Hal) molecular complexes: A natural bond orbital analysis

    Science.gov (United States)

    Isaev, A. N.

    2016-03-01

    Hydrogen bonded C-H···Y complexes formed by H2O, H2S molecules, hydrogen halides, and halogen-ions with methane, halogen substituted methane as well as with the C2H2 and NCH molecules were studied at the MP2/aug-cc-pVDZ level. The structure of NBOs corresponding to lone pair of acceptor Y, n Y, and vacant anti-σ-bond C-H of proton donor was analyzed and estimates of second order perturbation energy E(2) characterizing donor-acceptor n Y → σ C-H * charge-transfer interaction were obtained. Computational results for complexes of methane and its halogen substituted derivatives show that for each set of analogous structures, the EnY→σ*C-H (2) energy tends to grow with an increase in the s-component percentage in the lone pair NBO of acceptor Y. Calculations for different C···Y distances show that the equilibrium geometries of complexes lie in the region where the E(2) energy is highest and it changes symbatically with the length of the covalent E-H bond when the R(C···Y) distance is varied. The performed analysis allows us to divide the hydrogen bonded complexes into two groups, depending on the pattern of overlapping for NBOs of the hydrogen bridge.

  17. A Monte Carlo simulation study of associated liquid crystals

    Science.gov (United States)

    Berardi, R.; Fehervari, M.; Zannoni, C.

    We have performed a Monte Carlo simulation study of a system of ellipsoidal particles with donor-acceptor sites modelling complementary hydrogen-bonding groups in real molecules. We have considered elongated Gay-Berne particles with terminal interaction sites allowing particles to associate and form dimers. The changes in the phase transitions and in the molecular organization and the interplay between orientational ordering and dimer formation are discussed. Particle flip and dimer moves have been used to increase the convergency rate of the Monte Carlo (MC) Markov chain.

  18. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  19. The analysis of structural and electronic environments of silicon network in HWCVD deposited a-SiC:H films

    International Nuclear Information System (INIS)

    Swain, Bibhu P.

    2007-01-01

    Hydrogenated amorphous silicon carbon alloys (a-SiC:H) films were deposited by hot wire chemical vapour deposition (HWCVD) using SiH 4 and C 2 H 2 as precursor gases. a-SiC:H films were characterized by Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Solid-state plasmon of Si network shifts from 19.2 to 20.5 eV by varying C 2 H 2 flow rate from 2 to 10 sccm. Incorporation of carbon content changes the valence band structure and s orbital is more dominant than sp and p orbital with carbon incorporation

  20. Compositional study of glow-discharge A-SiC:H films for window layer of solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Imura, T; Hiraki, A

    1983-10-01

    A series of compositional studies on various types of amorphous silicon-carbon-hydrogen alloy (a-SiC:H) were performed by means of Auger electron spectroscopy (AES) and infrared spectroscopy (IR). The difference between CH4 and C2H4 as a carbon source was examined. From the infrared absorption study it is shown that C2H4-based a-SiC:H films contain carbons as -C2H5 and -CH3,, whereas CH4-based ones as tetrahedral atoms. These results will serve to elucidate the fabrication problems of solar cells. 14 references.

  1. P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds.

    Science.gov (United States)

    Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong

    2017-04-07

    An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

  2. Oxidative C-H/C-H Cross-Coupling Reactions between N-Acylanilines and Benzamides Enabled by a Cp*-Free RhCl3/TFA Catalytic System.

    Science.gov (United States)

    You, Jingsong; Shi, Yang; Zhang, Luoqiang; Lan, Jingbo; Zhang, Min; Zhou, Fulin; Wei, Wenlong

    2018-06-03

    Using the dual chelation-assisted strategy, a completely regiocontrolled oxidative C-H/C-H cross-coupling reaction between an N-acylaniline and a benzamide has been accomplished for the first time, which enables a step-economical and highly efficient pathway to 2-amino-2'-carboxybiaryl scaffolds from readily available substrates. A Cp*-free RhCl3/TFA catalytic system has been developed to replace the generally used [Cp*RhCl2]2/AgSbF6 (Cp* = pentamethyl cyclopentadienyl) in oxidative C-H/C-H cross-coupling reactions between two (hetero)arenes. The RhCl3/TFA system avoids the use of expensive Cp* ligand and AgSbF6. As an illustrative example, the protocol developed herein greatly streamlines access to naturally occurring benzo[c]phenanthridine alkaloid oxynitidine in an excellent overall yield. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Bayesian Monte Carlo method

    International Nuclear Information System (INIS)

    Rajabalinejad, M.

    2010-01-01

    To reduce cost of Monte Carlo (MC) simulations for time-consuming processes, Bayesian Monte Carlo (BMC) is introduced in this paper. The BMC method reduces number of realizations in MC according to the desired accuracy level. BMC also provides a possibility of considering more priors. In other words, different priors can be integrated into one model by using BMC to further reduce cost of simulations. This study suggests speeding up the simulation process by considering the logical dependence of neighboring points as prior information. This information is used in the BMC method to produce a predictive tool through the simulation process. The general methodology and algorithm of BMC method are presented in this paper. The BMC method is applied to the simplified break water model as well as the finite element model of 17th Street Canal in New Orleans, and the results are compared with the MC and Dynamic Bounds methods.

  4. Monte Carlo principles and applications

    Energy Technology Data Exchange (ETDEWEB)

    Raeside, D E [Oklahoma Univ., Oklahoma City (USA). Health Sciences Center

    1976-03-01

    The principles underlying the use of Monte Carlo methods are explained, for readers who may not be familiar with the approach. The generation of random numbers is discussed, and the connection between Monte Carlo methods and random numbers is indicated. Outlines of two well established Monte Carlo sampling techniques are given, together with examples illustrating their use. The general techniques for improving the efficiency of Monte Carlo calculations are considered. The literature relevant to the applications of Monte Carlo calculations in medical physics is reviewed.

  5. Contributon Monte Carlo

    International Nuclear Information System (INIS)

    Dubi, A.; Gerstl, S.A.W.

    1979-05-01

    The contributon Monte Carlo method is based on a new recipe to calculate target responses by means of volume integral of the contributon current in a region between the source and the detector. A comprehensive description of the method, its implementation in the general-purpose MCNP code, and results of the method for realistic nonhomogeneous, energy-dependent problems are presented. 23 figures, 10 tables

  6. Carlos Vesga Duarte

    Directory of Open Access Journals (Sweden)

    Pedro Medina Avendaño

    1981-01-01

    Full Text Available Carlos Vega Duarte tenía la sencillez de los seres elementales y puros. Su corazón era limpio como oro de aluvión. Su trato directo y coloquial ponía de relieve a un santandereano sin contaminaciones que amaba el fulgor de las armas y se encandilaba con el destello de las frases perfectas

  7. Fundamentals of Monte Carlo

    International Nuclear Information System (INIS)

    Wollaber, Allan Benton

    2016-01-01

    This is a powerpoint presentation which serves as lecture material for the Parallel Computing summer school. It goes over the fundamentals of the Monte Carlo calculation method. The material is presented according to the following outline: Introduction (background, a simple example: estimating @@), Why does this even work? (The Law of Large Numbers, The Central Limit Theorem), How to sample (inverse transform sampling, rejection), and An example from particle transport.

  8. Microcanonical Monte Carlo

    International Nuclear Information System (INIS)

    Creutz, M.

    1986-01-01

    The author discusses a recently developed algorithm for simulating statistical systems. The procedure interpolates between molecular dynamics methods and canonical Monte Carlo. The primary advantages are extremely fast simulations of discrete systems such as the Ising model and a relative insensitivity to random number quality. A variation of the algorithm gives rise to a deterministic dynamics for Ising spins. This model may be useful for high speed simulation of non-equilibrium phenomena

  9. Fundamentals of Monte Carlo

    Energy Technology Data Exchange (ETDEWEB)

    Wollaber, Allan Benton [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-06-16

    This is a powerpoint presentation which serves as lecture material for the Parallel Computing summer school. It goes over the fundamentals of the Monte Carlo calculation method. The material is presented according to the following outline: Introduction (background, a simple example: estimating π), Why does this even work? (The Law of Large Numbers, The Central Limit Theorem), How to sample (inverse transform sampling, rejection), and An example from particle transport.

  10. CERN honours Carlo Rubbia

    CERN Multimedia

    2009-01-01

    On 7 April CERN will be holding a symposium to mark the 75th birthday of Carlo Rubbia, who shared the 1984 Nobel Prize for Physics with Simon van der Meer for contributions to the discovery of the W and Z bosons, carriers of the weak interaction. Following a presentation by Rolf Heuer, lectures will be given by eminent speakers on areas of science to which Carlo Rubbia has made decisive contributions. Michel Spiro, Director of the French National Institute of Nuclear and Particle Physics (IN2P3) of the CNRS, Lyn Evans, sLHC Project Leader, and Alan Astbury of the TRIUMF Laboratory will talk about the physics of the weak interaction and the discovery of the W and Z bosons. Former CERN Director-General Herwig Schopper will lecture on CERN’s accelerators from LEP to the LHC. Giovanni Bignami, former President of the Italian Space Agency and Professor at the IUSS School for Advanced Studies in Pavia will speak about his work with Carlo Rubbia. Finally, Hans Joachim Sch...

  11. CERN honours Carlo Rubbia

    CERN Multimedia

    2009-01-01

    On 7 April CERN will be holding a symposium to mark the 75th birthday of Carlo Rubbia, who shared the 1984 Nobel Prize for Physics with Simon van der Meer for contributions to the discovery of the W and Z bosons, carriers of the weak interaction. Following a presentation by Rolf Heuer, lectures will be given by eminent speakers on areas of science to which Carlo Rubbia has made decisive contributions. Michel Spiro, Director of the French National Institute of Nuclear and Particle Physics (IN2P3) of the CNRS, Lyn Evans, sLHC Project Leader, and Alan Astbury of the TRIUMF Laboratory will talk about the physics of the weak interaction and the discovery of the W and Z bosons. Former CERN Director-General Herwig Schopper will lecture on CERN’s accelerators from LEP to the LHC. Giovanni Bignami, former President of the Italian Space Agency, will speak about his work with Carlo Rubbia. Finally, Hans Joachim Schellnhuber of the Potsdam Institute for Climate Research and Sven Kul...

  12. Who Writes Carlos Bulosan?

    Directory of Open Access Journals (Sweden)

    Charlie Samuya Veric

    2001-12-01

    Full Text Available The importance of Carlos Bulosan in Filipino and Filipino-American radical history and literature is indisputable. His eminence spans the pacific, and he is known, diversely, as a radical poet, fictionist, novelist, and labor organizer. Author of the canonical America Iis the Hearts, Bulosan is celebrated for chronicling the conditions in America in his time, such as racism and unemployment. In the history of criticism on Bulosan's life and work, however, there is an undeclared general consensus that views Bulosan and his work as coherent permanent texts of radicalism and anti-imperialism. Central to the existence of such a tradition of critical reception are the generations of critics who, in more ways than one, control the discourse on and of Carlos Bulosan. This essay inquires into the sphere of the critical reception that orders, for our time and for the time ahead, the reading and interpretation of Bulosan. What eye and seeing, the essay asks, determine the perception of Bulosan as the angel of radicalism? What is obscured in constructing Bulosan as an immutable figure of the political? What light does the reader conceive when the personal is brought into the open and situated against the political? the essay explores the answers to these questions in Bulosan's loving letters to various friends, strangers, and white American women. The presence of these interrogations, the essay believes, will secure ultimately the continuing importance of Carlos Bulosan to radical literature and history.

  13. Monte Carlo alpha calculation

    Energy Technology Data Exchange (ETDEWEB)

    Brockway, D.; Soran, P.; Whalen, P.

    1985-01-01

    A Monte Carlo algorithm to efficiently calculate static alpha eigenvalues, N = ne/sup ..cap alpha..t/, for supercritical systems has been developed and tested. A direct Monte Carlo approach to calculating a static alpha is to simply follow the buildup in time of neutrons in a supercritical system and evaluate the logarithmic derivative of the neutron population with respect to time. This procedure is expensive, and the solution is very noisy and almost useless for a system near critical. The modified approach is to convert the time-dependent problem to a static ..cap alpha../sup -/eigenvalue problem and regress ..cap alpha.. on solutions of a/sup -/ k/sup -/eigenvalue problem. In practice, this procedure is much more efficient than the direct calculation, and produces much more accurate results. Because the Monte Carlo codes are intrinsically three-dimensional and use elaborate continuous-energy cross sections, this technique is now used as a standard for evaluating other calculational techniques in odd geometries or with group cross sections.

  14. Tribological Performance of Hydrogenated Amorphous Carbon (a-C: H DLC Coating when Lubricated with Biodegradable Vegetal Canola Oil

    Directory of Open Access Journals (Sweden)

    H.M. Mobarak

    2014-06-01

    Full Text Available Increasing environmental awareness and demands for lowering energy consumptions are strong driving forces behind the development of the vehicles of tomorrow. Without the advances of lubricant chemistry and adequate lubricant formulation, expansion of modern engines would not have been possible. Considering environmental awareness factors as compared to mineral oils, vegetal oil based biolubricants are renewable, biodegradable, non-toxic and have a least amount of greenhouse gases. Furthermore, improvement in engine performance and transmission components, which were impossible to achieve by applying only lubricants design, is now possible through diamond like carbon (DLC coatings. DLC coatings exhibit brilliant tribological properties, such as good wear resistance and low friction. In this regard, tribological performance of a-C: H DLC coating when lubricated with Canola vegetal oil has been investigated by the help of a ball-on-flat geometry. Experimental results demonstrated that the a-C: H DLC coating exhibited better performance with Canola oil in terms of friction and wear as compared to the uncoated materials. Large amount of polar components in the Canola oil significantly improved the tribological properties of the a-C:H coating. Thus, usage of a-C: H DLC coating with Canola oil in the long run may have a positive impact on engine life.

  15. Copper-promoted methylene C-H oxidation to a ketone derivative by O2

    DEFF Research Database (Denmark)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J.

    2017-01-01

    stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions...

  16. A selective C-H insertion/olefination protocol for the synthesis of α-methylene-γ-butyrolactone natural products.

    Science.gov (United States)

    Lloyd, Matthew G; D'Acunto, Mariantonietta; Taylor, Richard J K; Unsworth, William P

    2016-02-07

    A regio- and stereoselective one-pot C-H insertion/olefination protocol has been developed for the late stage installation of α-methylene-γ-butyrolactones into conformationally restricted cyclohexanol-derivatives. The method has been successfully applied in the total synthesis of eudesmanolide natural product frameworks, including α-cyclocostunolide.

  17. Rh(iii)-catalyzed C-H olefination of N-pentafluoroaryl benzamides using air as the sole oxidant.

    Science.gov (United States)

    Lu, Yi; Wang, Huai-Wei; Spangler, Jillian E; Chen, Kai; Cui, Pei-Pei; Zhao, Yue; Sun, Wei-Yin; Yu, Jin-Quan

    2015-03-01

    The oxidative olefination of a broad array of arenes and heteroarenes with a variety of activated and unactivated olefins has be achieved via a rhodium(iii)-catalyzed C-H activation reaction. The use of an N -pentafluorophenyl benzamide directing group is crucial for achieving catalytic turnovers in the presence of air as the sole oxidant without using a co-oxidant.

  18. Palladium-Catalyzed C-H Functionalization Using Guanidine as a Directing Group: Ortho Arylation and Olefination of Arylguanidines

    Science.gov (United States)

    Shao, Jiaan; Chen, Wenteng; Giulianotti, Marc A.; Houghten, Richard A.; Yu, Yongping

    2012-01-01

    Palladium-catalyzed C-H functionalization using guanidine as the directing group was achieved under mild reaction conditions. Various guanidine derivatives were produced in moderate to good yields by using simple unactivated arenes or ethyl acrylate as the source of arylation or olefination respectively. PMID:23095022

  19. Palladium-catalyzed C-H olefination of uracils and caffeines using molecular oxygen as the sole oxidant.

    Science.gov (United States)

    Zhang, Xinyu; Su, Lv; Qiu, Lin; Fan, Zhenwei; Zhang, Xiaofeng; Lin, Shen; Huang, Qiufeng

    2017-04-18

    The palladium-catalyzed oxidative C-H olefination of uracils or caffeines with alkenes using an atmospheric pressure of molecular oxygen as the sole oxidant has been disclosed. This novel strategy offers an efficient and environmentally friendly method to biologically important C5-alkene uracil derivatives or C8-alkene caffeine derivatives.

  20. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2013-11-27

    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

  1. Activation of the C-H bond: catalytic hydroxylation of hydrocarbons by new cobaltic alkylperoxydic complexes; selective and catalytic cycloalkane dehydrogenation in presence of uranium for hydrogen transfer

    International Nuclear Information System (INIS)

    Brazi, E.

    1987-01-01

    The aim of the thesis is to improve efficiency and selectivity of chemical reactions for alkane transformations. In the first part decomposition of hydroperoxides and hydrocarbon hydroxylation by cobalt complexes is studied. In the second part cycloalkanes are dehydrogenated into aromatics with a Pt catalyst, trapping hydrogen by uranium. Uranium hydride UH 3 can yield very pure hydrogen at reasonable temperature [fr

  2. Magnetism, chemical bonding and hyperfine properties in the nanoscale antiferromagnet [Fe(O Me)2(O2 C C H2 Cl)]10

    International Nuclear Information System (INIS)

    Zeng, Z.; Duan, Y.; Guenzburger, Diana

    1996-09-01

    The electronic and magnetic properties of the nanometer-size antiferromagnet (the ferric wheel molecule) are investigated with the first-principles spin-polarized Discrete Variational Method, in the framework of Density Functional theory. Magnetic moments, densities of the states and charge and spin-density maps are obtained. The Moessbauer hyperfine parameters Isomer shift, Quadrupole Splitting and Hyperfine Field are obtained from the calculations and compared to reported experimental values when available. (author). 33 refs., 8 figs., 4 tabs

  3. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

    Science.gov (United States)

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

    2017-04-18

    We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C-H bond activation

    Science.gov (United States)

    Wang, Zhe-Chen; Yin, Shi; Bernstein, Elliot R.

    2013-11-01

    Both ceria (CeO2) and alumina (Al2O3) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), CexAlyOz, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C4H10) is studied. The very active species CeAlO4• can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other CexAlyOz NBONCs do not show reactivities toward CO and C4H10. The structures, as well as the reactivities, of CexAlyOz NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO4• NBONC possesses a kite-shaped structure with an OtCeObObAlOt configuration (Ot, terminal oxygen; Ob, bridging oxygen). An unpaired electron is localized on the Ot atom of the AlOt moiety rather than the CeOt moiety: this Ot centered radical moiety plays a very important role for the reactivity of the CeAlO4• NBONC. The reactivities of Ce2O4, CeAlO4•, and Al2O4 toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO4• with C4H10 to form the CeAlO4H•C4H9• encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of AlxOy/MmOn or MmOn/AlxOy materials are proposed consistent with the presented experimental and theoretical results.

  5. C-H and H-H Bond Activation via Ligand Dearomatization/Rearomatization of a PN3P-Rhodium(I) Complex

    KAUST Repository

    Huang, Kuo-Wei

    2015-04-13

    A neutral complex PN3P-Rh(I)Cl (2) was prepared from a reaction of the PN3P pincer ligand (1) with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene). Upon treatment with a suitable base, H–H and Csp2–H activation reactions can be achieved through the deprotonation/reprotonation of one of the N–H arms and dearomatization/rearomatization of the central pyridine ring with the oxidation state of Rh remaining I.

  6. Active groups for oxidative activation of C-H bond in C{sub 2}-C{sub 5} paraffins on V-P-O catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms by proton abstraction. A comparison of the results on n-butane and butenes oxidation over vanadyl pyrophosphate allowed to conclude that the paraffin oxidation did not take place due to the molecule dehydrogenation process at the first stage of its conversion. Up to now, more than 100 papers related to paraffins oxidation over vanadyl pyrophosphate and the physico-chemical properties of the catalyst have been published. The process of n-butane oxidation is realized in practice. But still, the question about the nature of active sites of the catalyst and the reaction mechanism remains open and provokes further investigations. The present paper deals with our opinion about the problem and the experimental results supporting it. (orig.)

  7. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa; Azzi, Joachim; Abou-Hamad, Edy; Anjum, Dalaver H.; Pasha, Fahran A.; Huang, Kuo-Wei; Emsley, Lyndon; Basset, Jean-Marie

    2013-01-01

    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

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

    Science.gov (United States)

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

    2018-02-02

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

  9. C-H and H-H Bond Activation via Ligand Dearomatization/Rearomatization of a PN3P-Rhodium(I) Complex

    KAUST Repository

    Huang, Kuo-Wei; Wang, Yuan; Zheng, Bin; Pan, Yupeng; Pan, Chengling; He, Lipeng

    2015-01-01

    A neutral complex PN3P-Rh(I)Cl (2) was prepared from a reaction of the PN3P pincer ligand (1) with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene). Upon treatment with a suitable base, H–H and Csp2–H activation reactions can be achieved through

  10. Combined UV-C/H2O2-VUV processes for the treatment of an actual slaughterhouse wastewater.

    Science.gov (United States)

    Naderi, Kambiz Vaezzadeh; Bustillo-Lecompte, Ciro Fernando; Mehrvar, Mehrab; Abdekhodaie, Mohammad Jafar

    2017-05-04

    In this study, a three-factor, three-level Box-Behnken design with response surface methodology were used to maximize the TOC removal and minimize the H 2 O 2 residual in the effluent of the combined UV-C/H 2 O 2 -VUV system for the treatment of an actual slaughterhouse wastewater (SWW) collected from one of the meat processing plants in Ontario, Canada. The irradiation time and the initial concentrations of total organic carbon (TOC o ) and hydrogen peroxide (H 2 O 2o ) were the three predictors, as independent variables, studied in the design of experiments. The multiple response approach was used to obtain desirability response surfaces at the optimum factor settings. Subsequently, the optimum conditions to achieve the maximum percentage TOC removal of 46.19% and minimum H 2 O 2 residual of 1.05% were TOC o of 213 mg L -1 , H 2 O 2o of 450 mg L -1 , and irradiation time of 9 min. The attained optimal operating conditions were validated with a complementary test. Consequently, the TOC removal of 45.68% and H 2 O 2 residual of 1.03% were achieved experimentally, confirming the statistical model reliability. Three individual processes, VUV alone, VUV/H 2 O 2 , and UV-C/H 2 O 2 , were also evaluated to compare their performance for the treatment of the actual SWW using the optimum parameters obtained in combined UV-C/H 2 O 2 -VUV processes. Results confirmed that an adequate combination of the UV-C/H 2 O 2 -VUV processes is essential for an optimized TOC removal and H 2 O 2 residual. Finally, respirometry analyses were also performed to evaluate the biodegradability of the SWW and the BOD removal efficiency of the combined UV-C/H 2 O 2 -VUV processes.

  11. Electrostatics determine vibrational frequency shifts in hydrogen bonded complexes.

    Science.gov (United States)

    Dey, Arghya; Mondal, Sohidul Islam; Sen, Saumik; Ghosh, Debashree; Patwari, G Naresh

    2014-12-14

    The red-shifts in the acetylenic C-H stretching vibration of C-H∙∙∙X (X = O, N) hydrogen-bonded complexes increase with an increase in the basicity of the Lewis base. Analysis of various components of stabilization energy suggests that the observed red-shifts are correlated with the electrostatic component of the stabilization energy, while the dispersion modulates the stabilization energy.

  12. Bonding and structure of copper nitrenes.

    Science.gov (United States)

    Cundari, Thomas R; Dinescu, Adriana; Kazi, Abul B

    2008-11-03

    Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (beta-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S = 1) is the ground state, CASSCF calculations indicate that a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond.

  13. Hard TiCx/SiC/a-C:H nanocomposite thin films using pulsed high energy density plasma focus device

    International Nuclear Information System (INIS)

    Umar, Z.A.; Rawat, R.S.; Tan, K.S.; Kumar, A.K.; Ahmad, R.; Hussain, T.; Kloc, C.; Chen, Z.; Shen, L.; Zhang, Z.

    2013-01-01

    Highlights: •The energetic ions and electron beams are used to synthesize TiC x /SiC/a-C:H films. •As-deposited crystalline and hard nanocomposite TiC x /SiC/a-C:H films are synthesized. •Very high average deposition rates of 68 nm/shot are achieved using dense plasma focus. •The maximum hardness of 22 GPa is achieved at the surface of the film. -- Abstract: Thin films of TiC x /SiC/a-C:H were synthesized on Si substrates using a complex mix of high energy density plasmas and instability accelerated energetic ions of filling gas species, emanated from hot and dense pinched plasma column, in dense plasma focus device. The conventional hollow copper anode of Mather type plasma focus device was replaced by solid titanium anode for synthesis of TiC x /SiC/a-C:H nanocomposite thin films using CH 4 :Ar admixture of (1:9, 3:7 and 5:5) for fixed 20 focus shots as well as with different number of focus shots with fixed CH 4 :Ar admixture ratio 3:7. XRD results showed the formation of crystalline TiC x /SiC phases for thin film synthesized using different number of focus shots with CH 4 :Ar admixture ratio fixed at 3:7. SEM results showed that the synthesized thin films consist of nanoparticle agglomerates and the size of agglomerates depended on the CH 4 :Ar admixture ratio as well as on the number of focus shots. Raman analysis showed the formation of polycrystalline/amorphous Si, SiC and a-C for different CH 4 :Ar ratio as well as for different number of focus shots. The XPS analysis confirmed the formation of TiC x /SiC/a-C:H composite thin film. Nanoindentation results showed that the hardness and elastic modulus values of composite thin films increased with increasing number of focus shots. Maximum values of hardness and elastic modulus at the surface of the composite thin film were found to be about 22 and 305 GPa, respectively for 30 focus shots confirming the successful synthesis of hard composite TiC x /SiC/a-C:H coatings

  14. Neutron diffraction study of phase relationship of Ti-C-H system

    International Nuclear Information System (INIS)

    Khidirov, I.; Mukhtarova, N.N.; Mirzaev, B.B.; Serikbaev, B.T.; Zaginaichenko, S.Yu.; Schur, D.V.; Pishuk, V.K.; Kuzmenko, L.V.; Garbuz, V.V.; Nuzhda, S.V.; Pishuk, O.V.

    2006-01-01

    temperature the sintering process is very active. Later on, the step increasing of temperature was carried out till 1000 deg. C with a step of 100 deg. C. The briquettes were exposed during 24 h at each temperature. With increasing temperature up to 800-1000 deg. C the pressured powder became well sintered and hydrogen emission from the sample was prevented. The final product was prepared after the annealing at 1000 deg. C followed by quenching in water. Compound of the samples was controlled by chemical analysis and compound of the single-phase samples also was controlled by minimizing the divergence factors of structure determination using neutron diffraction patterns. It is established that at hardening from 1000 deg. C in the samples with low concentration of C and H the solid solution of C and H in BCC β-Ti (with impurity of FCC- TiC x H y -phase) is formed. This metastable phase is stable enough at the room temperature. It is shown that at carbon concentration of 0.30 ≤ x ≤ 0.50 and y ≥ x in Ti-C-H system the ordered hexagonal close-packed (HCP) structure is stabilized, and at y x H y compounds have the ordered HCP structure corresponding to formula Ti 2 C 1-z H 2-z . The crystal structure of the phase is described within the framework of space group, where metal atoms are strongly displaced along c axis (Z Me =0.234±0.001) with respect to their ideal positions (z id =1/4). Step annealing of the single-phase solid solutions at temperatures of 700-600-500 deg. C during 24 h leads to decay of the samples, having concentration C/Ti≤0.43, the hydride phases being separated. Hence, the ordered solid solution Ti 2 C 1-x H 2-y is stable at concentrations 1.00≥C/Ti>0.43 (near carbon stoichiometry Ti 2 C), but it is metastable at concentrations 0.30≤C/T≤0.43. Compound TiC x H y at concentrations 0.45≤x≤0.55 and y< x can have both disordered (sp. gr. Fm3m) and ordered FCC-structure (sp. gr. Fd3m) depending on temperature. At temperatures lower than 600 deg. C

  15. Bonding with Your Baby

    Science.gov (United States)

    ... the future bonding of the child and parent. Adoptive parents may be concerned about bonding with their ... general emotional support. And it's OK to ask family members and friends for help in the days — ...

  16. Enhancement of Ti-containing hydrogenated carbon (Ti-C:H) films by high-power plasma-sputtering

    International Nuclear Information System (INIS)

    Gwo, Jyh; Chu, Chun-Lin; Tsai, Ming-Jui; Lee, Shyong

    2012-01-01

    Ti-containing amorphous hydrogenated carbon (Ti-C:H) thin films were deposited on stainless steel SS304 substrates by high-power pulsed magnetron sputtering (HPPMS) in an atmosphere of mixed Ar and C 2 H 2 gases using titanium metal as the cathodic material. The multilayer structure of the deposited film had a Ti-TiC-DLC gradient to improve adhesion and reduce residual stress. This study investigates the effects of substrate bias and target-to-substrate distance on the mechanical properties of Ti-C:H films. Film properties, including composition, morphology, microstructure, mechanical, and tribology, were examined by glow discharge spectroscopy (GDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and a nanoindenter and a pin-on-disk tribometer. Experiments revealed impressive results.

  17. Enhancement of Ti-containing hydrogenated carbon (Tisbnd C:H) films by high-power plasma-sputtering

    Science.gov (United States)

    Gwo, Jyh; Chu, Chun-Lin; Tsai, Ming-Jui; Lee, Shyong

    2012-02-01

    Ti-containing amorphous hydrogenated carbon (Tisbnd C:H) thin films were deposited on stainless steel SS304 substrates by high-power pulsed magnetron sputtering (HPPMS) in an atmosphere of mixed Ar and C2H2 gases using titanium metal as the cathodic material. The multilayer structure of the deposited film had a Tisbnd TiCsbnd DLC gradient to improve adhesion and reduce residual stress. This study investigates the effects of substrate bias and target-to-substrate distance on the mechanical properties of Tisbnd C:H films. Film properties, including composition, morphology, microstructure, mechanical, and tribology, were examined by glow discharge spectroscopy (GDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and a nanoindenter and a pin-on-disk tribometer. Experiments revealed impressive results.

  18. Amidines for versatile ruthenium(II)-catalyzed oxidative C-H activations with internal alkynes and acrylates.

    Science.gov (United States)

    Li, Jie; John, Michael; Ackermann, Lutz

    2014-04-25

    Cationic ruthenium complexes derived from KPF6 or AgOAc enabled efficient oxidative CH functionalizations on aryl and heteroaryl amidines. Thus, oxidative annulations of diversely decorated internal alkynes provided expedient access to 1-aminoisoquinolines, while catalyzed C-H activations with substituted acrylates gave rise to structurally novel 1-iminoisoindolines. The powerful ruthenium(II) catalysts displayed a remarkably high site-, regio- and, chemoselectivity. Therefore, the catalytic system proved tolerant of a variety of important electrophilic functional groups. Detailed mechanistic studies provided strong support for the cationic ruthenium(II) catalysts to operate by a facile, reversible C-H activation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Pärt: Collage sur B-A-C-H für Kammerorschester / Hans-Christian Dadelsen

    Index Scriptorium Estoniae

    Dadelsen, Hans-Christian

    1993-01-01

    Uuest heliplaadist "Pärt: Collage sur B-A-C-H für Kammerorschester, Summa (1991) für Streichorchester, Fratres, Sinfonie Nr. 2, Festina lente, Wenn Bach Bienen gezüchtet hätte, Credo für Klavier, Chor und Orchester. Philharmonia Orchestra and Chorus, Neeme Järvi". Chandos/Koch CD 9134 (WD: 63'02")

  20. Rh(III) -Catalyzed C-H Olefination of Benzoic Acids under Mild Conditions using Oxygen as the Sole Oxidant.

    Science.gov (United States)

    Jiang, Quandi; Zhu, Changlei; Zhao, Huaiqing; Su, Weiping

    2016-02-04

    Phthalide skeletons have been synthesized for the first time through a Rh(III) -catalyzed C-H olefination of benzoic acids under mild conditions using oxygen as the sole oxidant. Aromatic acids bearing a variety of functional groups could react with diverse alkenes to afford the desired cyclized lactones or uncyclized alkenylarenes in moderate-to-excellent yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Remote meta-C-H olefination of phenylacetic acids directed by a versatile U-shaped template.

    Science.gov (United States)

    Deng, Youqian; Yu, Jin-Quan

    2015-01-12

    meta-C-H olefination of phenylacetic acid derivatives has been achieved using a commercially available nitrile-containing template. The identification of N-formyl-protected glycine as the ligand (Formyl-Gly-OH) was crucial for the development of this reaction. Versatility of the template approach in accommodating macrocyclopalladation processes with different ring sizes is demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Australia's Bond Home Bias

    OpenAIRE

    Anil V. Mishra; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  3. Rats Born to Mothers Treated with Dexamethasone 15 cH Present Changes in Modulation of Inflammatory Process

    Directory of Open Access Journals (Sweden)

    Leoni V. Bonamin

    2012-01-01

    Full Text Available As little information about the effect of ultra high dilutions of glucocorticoid in reproduction is available in the literature, pregnant female Wistar rats (N=12 were blindly subcutaneously treated during all gestational and lactation period with: dexamethasone 4 mg/kg diluted into dexamethasone 15 cH (mixed; or dexamethasone 4 mg/kg diluted in water; or dexamethasone 15 cH, or vehicle. Parental generation had body weight, food and water consumption monitored. The F1 generation was monitored regarding to newborn development. No birth occurred in both groups treated with dexamethasone 4 mg/kg. After 60 days from birth, 12 male F1 rats were randomly selected from each remaining group and inoculated subcutaneously with 1% carrageenan into the footpad, for evaluation of inflammatory performance. Edema and histopathology of the footpad were evaluated, using specific staining methods, immunohistochemistry and digital histomorphometry. Mothers treated with mixed dexamethasone presented reduced water consumption. F1 rats born to dexamethasone 15 cH treated females presented significant increase in mast cell degranulation, decrease in monocyte percentage, increase in CD18+ PMN cells, and early expression of ED2 protein, in relation to control. The results show that the exposure of parental generation to highly diluted dexamethasone interferes in inflammation modulation in the F1 generation.

  4. Sensitivity of CLIC at 380 GeV to the top FCNC decay $t\\rightarrow cH$

    CERN Document Server

    AUTHOR|(SzGeCERN)442572

    2017-01-01

    In the Standard Model (SM), flavour changing neutral current (FCNC) top decays, possible at loop level only, are very strongly suppressed. Observation of any such decay would be a direct signature of physics beyond the SM. Large enhancements are possible in many "new physics" scenarios and the largest enhancement is in most cases expected for the $t\\rightarrow cH$ decay. A full study for CLIC was based on the WHIZARD simulation of FCNC top decays within the 2HDM(III) model. Beam polarization and beam-induced background were taken into account. Top pair production events with the FCNC decay $t\\rightarrow cH$ can be identified based on kinematic constrains and flavour tagging information. Due to a large overlap in the kinematic space with standard top pair events, the final signal selection-efficiency is small, at the 10% level. Expected limits on $BR(t\\rightarrow cH)\\times BR(H\\rightarrow b\\bar{b})$ are compared with earlier results based on parton level simulation.

  5. Superhard nanocomposite nc-TiC/a-C:H film fabricated by filtered cathodic vacuum arc technique

    International Nuclear Information System (INIS)

    Wang Yaohui; Zhang Xu; Wu Xianying; Zhang Huixing; Zhang Xiaoji

    2008-01-01

    Superhard nanocomposite nc-TiC/a-C:H films, with an excellent combination of high elastic recovery, low friction coefficient and good H/E ratio, were prepared by filtered cathodic vacuum arc technique using the C 2 H 2 gas as the precursor. The effect of C 2 H 2 flow rate on the microstructure, phase composition, mechanical and tribological properties of nanocomposite nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. It was observed that the C 2 H 2 flow rate significantly affected the Ti content and hardness of films. Furthermore, by selecting the proper value for C 2 H 2 flow rate, 20 sccm, one can deposit the nanocomposite film nc-TiC/a-C:H with excellent properties such as superhardness (66.4 GPa), high elastic recovery (83.3%) and high H/E ratio (0.13)

  6. Path integral Monte Carlo simulations of dense carbon-hydrogen plasmas

    Science.gov (United States)

    Zhang, Shuai; Militzer, Burkhard; Benedict, Lorin X.; Soubiran, François; Sterne, Philip A.; Driver, Kevin P.

    2018-03-01

    Carbon-hydrogen plasmas and hydrocarbon materials are of broad interest to laser shock experimentalists, high energy density physicists, and astrophysicists. Accurate equations of state (EOSs) of hydrocarbons are valuable for various studies from inertial confinement fusion to planetary science. By combining path integral Monte Carlo (PIMC) results at high temperatures and density functional theory molecular dynamics results at lower temperatures, we compute the EOSs for hydrocarbons from simulations performed at 1473 separate (ρ, T)-points distributed over a range of compositions. These methods accurately treat electronic excitation effects with neither adjustable parameter nor experimental input. PIMC is also an accurate simulation method that is capable of treating many-body interaction and nuclear quantum effects at finite temperatures. These methods therefore provide a benchmark-quality EOS that surpasses that of semi-empirical and Thomas-Fermi-based methods in the warm dense matter regime. By comparing our first-principles EOS to the LEOS 5112 model for CH, we validate the specific heat assumptions in this model but suggest that the Grüneisen parameter is too large at low temperatures. Based on our first-principles EOSs, we predict the principal Hugoniot curve of polystyrene to be 2%-5% softer at maximum shock compression than that predicted by orbital-free density functional theory and SESAME 7593. By investigating the atomic structure and chemical bonding of hydrocarbons, we show a drastic decrease in the lifetime of chemical bonds in the pressure interval from 0.4 to 4 megabar. We find the assumption of linear mixing to be valid for describing the EOS and the shock Hugoniot curve of hydrocarbons in the regime of partially ionized atomic liquids. We make predictions of the shock compression of glow-discharge polymers and investigate the effects of oxygen content and C:H ratio on its Hugoniot curve. Our full suite of first-principles simulation results may

  7. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  8. [Towards computer-aided catalyst design: Three effective core potential studies of C-H activation]. Final report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    Research in the initial grant period focused on computational studies relevant to the selective activation of methane, the prime component of natural gas. Reaction coordinates for methane activation by experimental models were delineated, as well as the bonding and structure of complexes that effect this important reaction. This research, highlighted in the following sections, also provided the impetus for further development, and application of methods for modeling metal-containing catalysts. Sections of the report describe the following: methane activation by multiple-bonded transition metal complexes; computational lanthanide chemistry; and methane activation by non-imido, multiple-bonded ligands.

  9. Monte Carlo Methods in Physics

    International Nuclear Information System (INIS)

    Santoso, B.

    1997-01-01

    Method of Monte Carlo integration is reviewed briefly and some of its applications in physics are explained. A numerical experiment on random generators used in the monte Carlo techniques is carried out to show the behavior of the randomness of various methods in generating them. To account for the weight function involved in the Monte Carlo, the metropolis method is used. From the results of the experiment, one can see that there is no regular patterns of the numbers generated, showing that the program generators are reasonably good, while the experimental results, shows a statistical distribution obeying statistical distribution law. Further some applications of the Monte Carlo methods in physics are given. The choice of physical problems are such that the models have available solutions either in exact or approximate values, in which comparisons can be mode, with the calculations using the Monte Carlo method. Comparison show that for the models to be considered, good agreement have been obtained

  10. Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes.

    Science.gov (United States)

    Zhao, Jincan; Fang, Hong; Han, Jianlin; Pan, Yi

    2014-05-02

    Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.

  11. Atomistic Monte Carlo Simulation of Lipid Membranes

    Directory of Open Access Journals (Sweden)

    Daniel Wüstner

    2014-01-01

    Full Text Available Biological membranes are complex assemblies of many different molecules of which analysis demands a variety of experimental and computational approaches. In this article, we explain challenges and advantages of atomistic Monte Carlo (MC simulation of lipid membranes. We provide an introduction into the various move sets that are implemented in current MC methods for efficient conformational sampling of lipids and other molecules. In the second part, we demonstrate for a concrete example, how an atomistic local-move set can be implemented for MC simulations of phospholipid monomers and bilayer patches. We use our recently devised chain breakage/closure (CBC local move set in the bond-/torsion angle space with the constant-bond-length approximation (CBLA for the phospholipid dipalmitoylphosphatidylcholine (DPPC. We demonstrate rapid conformational equilibration for a single DPPC molecule, as assessed by calculation of molecular energies and entropies. We also show transition from a crystalline-like to a fluid DPPC bilayer by the CBC local-move MC method, as indicated by the electron density profile, head group orientation, area per lipid, and whole-lipid displacements. We discuss the potential of local-move MC methods in combination with molecular dynamics simulations, for example, for studying multi-component lipid membranes containing cholesterol.

  12. Room-temperature Pd-catalyzed C-H chlorination by weak coordination: one-pot synthesis of 2-chlorophenols with excellent regioselectivity.

    Science.gov (United States)

    Sun, Xiuyun; Sun, Yonghui; Zhang, Chao; Rao, Yu

    2014-02-07

    A room-temperature Pd(II)-catalyzed regioselective chlorination reaction has been developed for a facile one-pot synthesis of a broad range of 2-chlorophenols. The reaction demonstrates an excellent regioselectivity and reactivity for C-H chlorination. This reaction represents one of the rare examples of mild C-H functionalization at ambient temperature.

  13. Reactivity of p-Toluenesulfonylmethyl Isocyanide: Iron-Involved C-H Tosylmethylation of Imidazopyridines in Nontoxic Media.

    Science.gov (United States)

    Lu, Shuai; Zhu, Xinju; Li, Ke; Guo, Yu-Jing; Wang, Meng-Dan; Zhao, Xue-Mei; Hao, Xin-Qi; Song, Mao-Ping

    2016-09-16

    A novel iron-involved tosylmethylation of imidazo[1,2-α]pyridines with p-toluenesulfonylmethyl isocyanide in a solvent mixture of H2O and PEG400 under an Ar atmosphere has been developed. This protocol provides a facile synthetic route for the functionalization of the imidazo[1,2-α]pyridine scaffold with broad substrate compatibility, which is less expensive and environmentally friendly. The current methodology could further enable regioselective C-H tosylmethylation of indole at the C3 position. Also, p-toluenesulfonylmethyl isocyanide was utilized as the tosylmethylating reagent for the first time.

  14. Transition Metal-Free Selective Double sp(3) C-H Oxidation of Cyclic Amines to 3-Alkoxyamine Lactams.

    Science.gov (United States)

    Osorio-Nieto, Urbano; Chamorro-Arenas, Delfino; Quintero, Leticia; Höpfl, Herbert; Sartillo-Piscil, Fernando

    2016-09-16

    The first chemical method for selective dual sp(3) C-H functionalization at the alpha-and beta positions of cyclic amines to their corresponding 3-alkoxyamine lactams is reported. Unlike traditional Cα-H oxidation of amines to amides mediated by transition metals, the present protocol, which involves the use of NaClO2/TEMPO/NaClO in either aqueous or organic solvent, not only allows the Cα-H oxidation but also the subsequent functionalization of the unreactive β-methylene group in an unprecedented tandem fashion and using environmentally friendly reactants.

  15. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.

    Science.gov (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng

    2018-03-07

    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The pseudohydrogen bond structures between 2-F-epoxy-butane and three kinds of bimolecular

    International Nuclear Information System (INIS)

    Liu Yanzhi; Yuan Kun; Lu Lingling; Zhu Yuancheng; Dong Xiaoning

    2012-01-01

    The weak intermolecular interactions between 2-F-epoxy-butane and Iminazole, Thiazole and Oxazole were theoretically discussed by using density functional B3LYP (Becke, three-parameter, Lee- Yang-Parr)/6-311++G ** and HF (Hartree Fock)/6-311++G ** methods. The results showed that both the N…H conventional hydrogen bond and C-F…H-C pseudohydrogen bond (PHB) structures are coexisting in the three complexes. The weak intermolecular interactions energies indicate the relative stabilities of the three complexes are proportionable. The calculated results showed that the stretch vibrational frequency of C-H bond (electronic acceptor) presents blue shift, but that of C-F bond, which is intensely related to F group (electronic donor), presents red shift. Electron density topological properties demonstrates that the covalent and ionic characteristics of the C-F…H-C pseudohydrogen bond are proportional to that of convention hydrogen bond. (authors)

  17. Lectures on Monte Carlo methods

    CERN Document Server

    Madras, Neal

    2001-01-01

    Monte Carlo methods form an experimental branch of mathematics that employs simulations driven by random number generators. These methods are often used when others fail, since they are much less sensitive to the "curse of dimensionality", which plagues deterministic methods in problems with a large number of variables. Monte Carlo methods are used in many fields: mathematics, statistics, physics, chemistry, finance, computer science, and biology, for instance. This book is an introduction to Monte Carlo methods for anyone who would like to use these methods to study various kinds of mathemati

  18. BONDING ALUMINUM METALS

    Science.gov (United States)

    Noland, R.A.; Walker, D.E.

    1961-06-13

    A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

  19. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

    Science.gov (United States)

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

    2017-04-19

    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane- and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines was evaluated.

  20. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  1. Advanced Multilevel Monte Carlo Methods

    KAUST Repository

    Jasra, Ajay; Law, Kody; Suciu, Carina

    2017-01-01

    This article reviews the application of advanced Monte Carlo techniques in the context of Multilevel Monte Carlo (MLMC). MLMC is a strategy employed to compute expectations which can be biased in some sense, for instance, by using the discretization of a associated probability law. The MLMC approach works with a hierarchy of biased approximations which become progressively more accurate and more expensive. Using a telescoping representation of the most accurate approximation, the method is able to reduce the computational cost for a given level of error versus i.i.d. sampling from this latter approximation. All of these ideas originated for cases where exact sampling from couples in the hierarchy is possible. This article considers the case where such exact sampling is not currently possible. We consider Markov chain Monte Carlo and sequential Monte Carlo methods which have been introduced in the literature and we describe different strategies which facilitate the application of MLMC within these methods.

  2. Advanced Multilevel Monte Carlo Methods

    KAUST Repository

    Jasra, Ajay

    2017-04-24

    This article reviews the application of advanced Monte Carlo techniques in the context of Multilevel Monte Carlo (MLMC). MLMC is a strategy employed to compute expectations which can be biased in some sense, for instance, by using the discretization of a associated probability law. The MLMC approach works with a hierarchy of biased approximations which become progressively more accurate and more expensive. Using a telescoping representation of the most accurate approximation, the method is able to reduce the computational cost for a given level of error versus i.i.d. sampling from this latter approximation. All of these ideas originated for cases where exact sampling from couples in the hierarchy is possible. This article considers the case where such exact sampling is not currently possible. We consider Markov chain Monte Carlo and sequential Monte Carlo methods which have been introduced in the literature and we describe different strategies which facilitate the application of MLMC within these methods.

  3. TARC: Carlo Rubbia's Energy Amplifier

    CERN Multimedia

    Laurent Guiraud

    1997-01-01

    Transmutation by Adiabatic Resonance Crossing (TARC) is Carlo Rubbia's energy amplifier. This CERN experiment demonstrated that long-lived fission fragments, such as 99-TC, can be efficiently destroyed.

  4. Monte Carlo simulation for IRRMA

    International Nuclear Information System (INIS)

    Gardner, R.P.; Liu Lianyan

    2000-01-01

    Monte Carlo simulation is fast becoming a standard approach for many radiation applications that were previously treated almost entirely by experimental techniques. This is certainly true for Industrial Radiation and Radioisotope Measurement Applications - IRRMA. The reasons for this include: (1) the increased cost and inadequacy of experimentation for design and interpretation purposes; (2) the availability of low cost, large memory, and fast personal computers; and (3) the general availability of general purpose Monte Carlo codes that are increasingly user-friendly, efficient, and accurate. This paper discusses the history and present status of Monte Carlo simulation for IRRMA including the general purpose (GP) and specific purpose (SP) Monte Carlo codes and future needs - primarily from the experience of the authors

  5. Adjoint electron Monte Carlo calculations

    International Nuclear Information System (INIS)

    Jordan, T.M.

    1986-01-01

    Adjoint Monte Carlo is the most efficient method for accurate analysis of space systems exposed to natural and artificially enhanced electron environments. Recent adjoint calculations for isotropic electron environments include: comparative data for experimental measurements on electronics boxes; benchmark problem solutions for comparing total dose prediction methodologies; preliminary assessment of sectoring methods used during space system design; and total dose predictions on an electronics package. Adjoint Monte Carlo, forward Monte Carlo, and experiment are in excellent agreement for electron sources that simulate space environments. For electron space environments, adjoint Monte Carlo is clearly superior to forward Monte Carlo, requiring one to two orders of magnitude less computer time for relatively simple geometries. The solid-angle sectoring approximations used for routine design calculations can err by more than a factor of 2 on dose in simple shield geometries. For critical space systems exposed to severe electron environments, these potential sectoring errors demand the establishment of large design margins and/or verification of shield design by adjoint Monte Carlo/experiment

  6. Monte Carlo theory and practice

    International Nuclear Information System (INIS)

    James, F.

    1987-01-01

    Historically, the first large-scale calculations to make use of the Monte Carlo method were studies of neutron scattering and absorption, random processes for which it is quite natural to employ random numbers. Such calculations, a subset of Monte Carlo calculations, are known as direct simulation, since the 'hypothetical population' of the narrower definition above corresponds directly to the real population being studied. The Monte Carlo method may be applied wherever it is possible to establish equivalence between the desired result and the expected behaviour of a stochastic system. The problem to be solved may already be of a probabilistic or statistical nature, in which case its Monte Carlo formulation will usually be a straightforward simulation, or it may be of a deterministic or analytic nature, in which case an appropriate Monte Carlo formulation may require some imagination and may appear contrived or artificial. In any case, the suitability of the method chosen will depend on its mathematical properties and not on its superficial resemblance to the problem to be solved. The authors show how Monte Carlo techniques may be compared with other methods of solution of the same physical problem

  7. Cohesion energetics of carbon allotropes: Quantum Monte Carlo study

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Hyeondeok; Kang, Sinabro; Koo, Jahyun; Lee, Hoonkyung; Kwon, Yongkyung, E-mail: ykwon@konkuk.ac.kr [Division of Quantum Phases and Devices, School of Physics, Konkuk University, Seoul 143-701 (Korea, Republic of); Kim, Jeongnim, E-mail: jnkim@ornl.gov [Materials Science and Technology Division and Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2014-03-21

    We have performed quantum Monte Carlo calculations to study the cohesion energetics of carbon allotropes, including sp{sup 3}-bonded diamond, sp{sup 2}-bonded graphene, sp–sp{sup 2} hybridized graphynes, and sp-bonded carbyne. The computed cohesive energies of diamond and graphene are found to be in excellent agreement with the corresponding values determined experimentally for diamond and graphite, respectively, when the zero-point energies, along with the interlayer binding in the case of graphite, are included. We have also found that the cohesive energy of graphyne decreases systematically as the ratio of sp-bonded carbon atoms increases. The cohesive energy of γ-graphyne, the most energetically stable graphyne, turns out to be 6.766(6) eV/atom, which is smaller than that of graphene by 0.698(12) eV/atom. Experimental difficulty in synthesizing graphynes could be explained by their significantly smaller cohesive energies. Finally, we conclude that the cohesive energy of a newly proposed graphyne can be accurately estimated with the carbon–carbon bond energies determined from the cohesive energies of graphene and three different graphynes considered here.

  8. Cohesion Energetics of Carbon Allotropes: Quantum Monte Carlo Study

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Hyeondeok [Konkuk University, South Korea; Kang, Sinabro [Konkuk University, South Korea; Koo, Jahyun [Konkuk University, South Korea; Lee, Hoonkyung [Konkuk University, South Korea; Kim, Jeongnim [ORNL; Kwon, Yongkyung [Konkuk University, South Korea

    2014-01-01

    We have performed quantum Monte Carlo calculations to study the cohesion energetics of carbon allotropes, including sp3-bonded diamond, sp2-bonded graphene, sp-sp2 hybridized graphynes, and sp-bonded carbyne. The comput- ed cohesive energies of diamond and graphene are found to be in excellent agreement with the corresponding values de- termined experimentally for diamond and graphite, respectively, when the zero-point energies, along with the interlayer binding in the case of graphite, are included. We have also found that the cohesive energy of graphyne decreases system- atically as the ratio of sp-bonded carbon atoms increases. The cohesive energy of -graphyne, the most energetically- stable graphyne, turns out to be 6.766(6) eV/atom, which is smaller than that of graphene by 0.698(12) eV/atom. Experi- mental difficulty in synthesizing graphynes could be explained by their significantly smaller cohesive energies. Finally we conclude that the cohesive energy of a newly-proposed two-dimensional carbon network can be accurately estimated with the carbon-carbon bond energies determined from the cohesive energies of graphene and three different graphynes.

  9. Palladium-Catalyzed ortho C-H Arylation of Benzaldehydes Using ortho-Sulfinyl Aniline Transient Auxiliary.

    Science.gov (United States)

    Mu, Delong; He, Gang; Chen, Gong

    2018-05-03

    A PdII-catalyzed ortho-(Csp2)-H arylation reaction of benzaldehydes using catalytic amount of 2-methylsulfinyl-aniline as transient auxiliary was developed. This reaction is compatible with a broad range of benzaldehyde and aryl iodide substrates. Compared with other related reaction systems, an excellent regioselectivity for ortho-C(sp2)-H bonds over benzylic C(sp3)-H bonds was obtained for ortho-alkyl-benzaldehyde substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik

    2012-01-01

    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...

  11. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...

  12. Topology of charge density of flucytosine and related molecules and characteristics of their bond charge distributions.

    Science.gov (United States)

    Murgich, Juan; Franco, Héctor J; San-Blas, Gioconda

    2006-08-24

    The molecular charge distribution of flucytosine (4-amino-5-fluoro-2-pyrimidone), uracil, 5-fluorouracil, and thymine was studied by means of density functional theory calculations (DFT). The resulting distributions were analyzed by means of the atoms in molecules (AIM) theory. Bonds were characterized through vectors formed with the charge density value, its Laplacian, and the bond ellipticity calculated at the bond critical point (BCP). Within each set of C=O, C-H, and N-H bonds, these vectors showed little dispersion. C-C bonds formed three different subsets, one with a significant degree of double bonding, a second corresponding to single bonds with a finite ellipticity produced by hyperconjugation, and a third one formed by a pure single bond. In N-C bonds, a decrease in bond length (an increase in double bond character) was not reflected as an increase in their ellipticity, as in all C-C bonds studied. It was also found that substitution influenced the N-C, C-O, and C-C bond ellipticity much more than density and its Laplacian at the BCP. The Laplacian of charge density pointed to the existence of both bonding and nonbonding maxima in the valence shell charge concentration of N, O, and F, while only bonding ones were found for the C atoms. The nonbonding maxima related to the sites for electrophilic attack and H bonding in O and N, while sites of nucleophilic attack were suggested by the holes in the valence shell of the C atoms of the carbonyl groups.

  13. N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.

    Science.gov (United States)

    Osberger, Thomas J; White, M Christina

    2014-08-06

    A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

  14. Dual C-H functionalization of N-aryl amines: synthesis of polycyclic amines via an oxidative Povarov approach.

    Science.gov (United States)

    Min, Chang; Sanchawala, Abbas; Seidel, Daniel

    2014-05-16

    Iminium ions generated in situ via copper(I) bromide catalyzed oxidation of N-aryl amines readily undergo [4 + 2] cycloadditions with a range of dienophiles. This method involves the functionalization of both a C(sp(3))-H and a C(sp(2))-H bond and enables the rapid construction of polycyclic amines under relatively mild conditions.

  15. Microwave-assisted extraction and a new determination method for total steroid saponins from Dioscorea zingiberensis C.H. Wright.

    Science.gov (United States)

    Ren, Yao; Chen, Yu; Hu, Bohan; Wu, Hui; Lai, Furao; Li, Xiaofeng

    2015-12-01

    An efficient microwave-assisted extraction (MAE) technique was applied to isolate total steroid saponins from Dioscorea zingiberensis C.H. Wright (DZW). The optimal extracting conditions were established as 75% ethanol as solvent, ratio of solid/liquid 1:20 (g/ml), temperature 75 °C, irradiation power 600 W and three extraction cycles of 6 min each. Scanning electron microscopy (SEM) images of DZW processed by four different extractions provided visual evidence of the disruption effect on DZW. Diosgenin was quantified by HPLC and examined further by LC-ESI/MS after acid hydrolysis. Total steroid saponins were calculated using diosgenin from total steroid saponins. The MAE procedure was optimized, validated and compared with other conventional extraction processes. This report provides a convenient technology for the extraction and quantification of total saponins of DZW combining MAE with HPLC and LC-ESI/MS for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. Fields, particles and analyticity: recent results or 30 goldberg (ER) variations on B.A.C.H

    International Nuclear Information System (INIS)

    Bros, J.

    1991-01-01

    As it is known, Axiomatic Field Theory (A) implies double analyticity of the η-point functions in space-time and energy-momentum Complex Variables (C), with various interconnections by Fourier-Laplace analysis. When the latter is replaced by. Harmonic Analysis (H) on spheres and hyperboloids, a new kind of double analyticity results from (A) (i.e. from locality, spectral condition, temperateness and invariance): complex angular momentum is thereby introduced (a missing chapter in (A)). Exploitation of Asymptotic Completeness via Bethe-Salpeter-type equations (B) leads to new developments of the previous theme on (A, C, H) (complex angular momentum) and of other themes on (A,C) (crossing, Haag-Swieca property etc...). Various aspects of (A) + (B) have been implemented in Constructive Field Theory (composite spectrum, asymptotic properties etc...) by a combination of specific techniques and of model-independent methods

  17. Fields, particles and analyticity: recent results or 30 goldberg (ER) variations on B.A.C.H

    Energy Technology Data Exchange (ETDEWEB)

    Bros, J

    1992-12-31

    As it is known, Axiomatic Field Theory (A) implies double analyticity of the {eta}-point functions in space-time and energy-momentum Complex Variables (C), with various interconnections by Fourier-Laplace analysis. When the latter is replaced by. Harmonic Analysis (H) on spheres and hyperboloids, a new kind of double analyticity results from (A) (i.e. from locality, spectral condition, temperateness and invariance): complex angular momentum is thereby introduced (a missing chapter in (A)). Exploitation of Asymptotic Completeness via Bethe-Salpeter-type equations (B) leads to new developments of the previous theme on (A, C, H) (complex angular momentum) and of other themes on (A,C) (crossing, Haag-Swieca property etc...). Various aspects of (A) + (B) have been implemented in Constructive Field Theory (composite spectrum, asymptotic properties etc...) by a combination of specific techniques and of model-independent methods.

  18. Multilevel sequential Monte Carlo samplers

    KAUST Repository

    Beskos, Alexandros; Jasra, Ajay; Law, Kody; Tempone, Raul; Zhou, Yan

    2016-01-01

    In this article we consider the approximation of expectations w.r.t. probability distributions associated to the solution of partial differential equations (PDEs); this scenario appears routinely in Bayesian inverse problems. In practice, one often has to solve the associated PDE numerically, using, for instance finite element methods which depend on the step-size level . hL. In addition, the expectation cannot be computed analytically and one often resorts to Monte Carlo methods. In the context of this problem, it is known that the introduction of the multilevel Monte Carlo (MLMC) method can reduce the amount of computational effort to estimate expectations, for a given level of error. This is achieved via a telescoping identity associated to a Monte Carlo approximation of a sequence of probability distributions with discretization levels . ∞>h0>h1⋯>hL. In many practical problems of interest, one cannot achieve an i.i.d. sampling of the associated sequence and a sequential Monte Carlo (SMC) version of the MLMC method is introduced to deal with this problem. It is shown that under appropriate assumptions, the attractive property of a reduction of the amount of computational effort to estimate expectations, for a given level of error, can be maintained within the SMC context. That is, relative to exact sampling and Monte Carlo for the distribution at the finest level . hL. The approach is numerically illustrated on a Bayesian inverse problem. © 2016 Elsevier B.V.

  19. Multilevel sequential Monte Carlo samplers

    KAUST Repository

    Beskos, Alexandros

    2016-08-29

    In this article we consider the approximation of expectations w.r.t. probability distributions associated to the solution of partial differential equations (PDEs); this scenario appears routinely in Bayesian inverse problems. In practice, one often has to solve the associated PDE numerically, using, for instance finite element methods which depend on the step-size level . hL. In addition, the expectation cannot be computed analytically and one often resorts to Monte Carlo methods. In the context of this problem, it is known that the introduction of the multilevel Monte Carlo (MLMC) method can reduce the amount of computational effort to estimate expectations, for a given level of error. This is achieved via a telescoping identity associated to a Monte Carlo approximation of a sequence of probability distributions with discretization levels . ∞>h0>h1⋯>hL. In many practical problems of interest, one cannot achieve an i.i.d. sampling of the associated sequence and a sequential Monte Carlo (SMC) version of the MLMC method is introduced to deal with this problem. It is shown that under appropriate assumptions, the attractive property of a reduction of the amount of computational effort to estimate expectations, for a given level of error, can be maintained within the SMC context. That is, relative to exact sampling and Monte Carlo for the distribution at the finest level . hL. The approach is numerically illustrated on a Bayesian inverse problem. © 2016 Elsevier B.V.

  20. Phase transition in nonuniform Josephson arrays: Monte Carlo simulations

    Science.gov (United States)

    Lozovik, Yu. E.; Pomirchy, L. M.

    1994-01-01

    Disordered 2D system with Josephson interactions is considered. Disordered XY-model describes the granular films, Josephson arrays etc. Two types of disorder are analyzed: (1) randomly diluted system: Josephson coupling constants J ij are equal to J with probability p or zero (bond percolation problem); (2) coupling constants J ij are positive and distributed randomly and uniformly in some interval either including the vicinity of zero or apart from it. These systems are simulated by Monte Carlo method. Behaviour of potential energy, specific heat, phase correlation function and helicity modulus are analyzed. The phase diagram of the diluted system in T c-p plane is obtained.

  1. On the physical origin of blue-shifted hydrogen bonds.

    Science.gov (United States)

    Li, Xiaosong; Liu, Lei; Schlegel, H Bernhard

    2002-08-14

    For blue-shifted hydrogen-bonded systems, the hydrogen stretching frequency increases rather than decreases on complexation. In computations at various levels of theory, the blue-shift in the archetypical system, F(3)C-H.FH, is reproduced at the Hartree-Fock level, indicating that electron correlation is not the primary cause. Calculations also demonstrate that a blue-shift does not require either a carbon center or the absence of a lone pair on the proton donor, because F(3)Si-H.OH(2), F(2)NH.FH, F(2)PH.NH(3), and F(2)PH.OH(2) have substantial blue-shifts. Orbital interactions are shown to lengthen the X-H bond and lower its vibrational frequency, and thus cannot be the source of the blue-shift. In the F(3)CH.FH system, the charge redistribution in F(3)CH can be reproduced very well by replacing the FH with a simple dipole, which suggests that the interactions are predominantly electrostatic. When modeled with a point charge for the proton acceptor, attractive electrostatic interactions elongate the F(3)C-H, while repulsive interactions shorten it. At the equilibrium geometry of a hydrogen-bonded complex, the electrostatic attraction between the dipole moments of the proton donor and proton acceptor must be balanced by the Pauli repulsion between the two fragments. In the absence of orbital interactions that cause bond elongation, this repulsive interaction leads to compression of the X-H bond and a blue-shift in its vibrational frequency.

  2. Rh(V) -Nitrenoid as a Key Intermediate in Rh(III) -Catalyzed Heterocyclization by C-H Activation: A Computational Perspective on the Cycloaddition of Benzamide and Diazo Compounds.

    Science.gov (United States)

    Zhou, Tao; Guo, Wei; Xia, Yuanzhi

    2015-06-15

    A mechanistic study of the substituent-dependent ring formations in Rh(III) -catalyzed C-H activation/cycloaddition of benzamide and diazo compounds was carried out by using DFT calculations. The results indicated that the decomposition of the diazo is facilitated upon the formation of the five-membered rhodacycle, in which the Rh(III) center is more electrophilic. The insertion of carbenoid into Rh-C(phenyl) bond occurs readily and forms a 6-membered rhodacycle, however, the following C-N bond formation is difficult both kinetically and thermodynamically by reductive elimination from the Rh(III) species. Instead, the Rh(V) -nitrenoid intermediate could be formed by migration of the pivalate from N to Rh, which undergoes the heterocyclization much more easily and complementary ring-formations could be modulated by the nature of the substituent at the α-carbon. When a vinyl is attached, the stepwise 1,3-allylic migration occurs prior to the pivalate migration and the 8-membered ring product will be formed. On the other hand, the pivalate migration becomes more favorable for the phenyl-contained intermediate because of the difficult 1,3-allylic migration accompanied by dearomatization, thus the 5-membered ring product was formed selectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Bond markets in Africa

    Directory of Open Access Journals (Sweden)

    Yibin Mu

    2013-07-01

    Full Text Available African bond markets have been steadily growing in recent years, but nonetheless remain undeveloped. African countries would benefit from greater access to financing and deeper financial markets. This paper compiles a unique set of data on government securities and corporate bond markets in Africa. It then applies an econometric model to analyze the key determinants of African government securities market and corporate bond market capitalization. Government securities market capitalization is directly related to better institutions and interest rate volatility, and inversely related to smaller fiscal deficits, higher interest rate spreads, exchange rate volatility, and current and capital account openness. Corporate bond market capitalization is directly linked to economic size, the level of development of the economy and financial markets, better institutions, and interest rate volatility, and inversely related to higher interest rate spreads and current account openness. Policy implications follow.

  4. Strategije drevesnega preiskovanja Monte Carlo

    OpenAIRE

    VODOPIVEC, TOM

    2018-01-01

    Po preboju pri igri go so metode drevesnega preiskovanja Monte Carlo (ang. Monte Carlo tree search – MCTS) sprožile bliskovit napredek agentov za igranje iger: raziskovalna skupnost je od takrat razvila veliko variant in izboljšav algoritma MCTS ter s tem zagotovila napredek umetne inteligence ne samo pri igrah, ampak tudi v številnih drugih domenah. Čeprav metode MCTS združujejo splošnost naključnega vzorčenja z natančnostjo drevesnega preiskovanja, imajo lahko v praksi težave s počasno konv...

  5. Handbook of wafer bonding

    CERN Document Server

    Ramm, Peter; Taklo, Maaike M V

    2011-01-01

    Written by an author and editor team from microsystems companies and industry-near research organizations, this handbook and reference presents dependable, first-hand information on bonding technologies.In the first part, researchers from companies and institutions around the world discuss the most reliable and reproducible technologies for the production of bonded wafers. The second part is devoted to current and emerging applications, including microresonators, biosensors and precise measuring devices.

  6. Diffusion bonding techniques

    International Nuclear Information System (INIS)

    Peters, R.D.

    1978-01-01

    The applications of diffusion bonding at the General Electric Neutron Devices Department are briefly discussed, with particular emphasis on the gold/gold or gold/indium joints made between metallized alumina ceramic parts in the vacuum switch tube and the crystal resonator programs. Fixtures which use the differential expansion of dissimilar metals are described and compared to one that uses hydraulic pressure to apply the necessary bonding force

  7. Binding of hydrocarbons and other extremely weak ligands to transition metal complexes that coordinate hydrogen: Investigation of cis-interactions and delocalized bonding involving sigma bonds

    International Nuclear Information System (INIS)

    Kubas, G.J.; Eckert, J.; Luo, X.L.

    1997-01-01

    This is the final report of a three-year Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). At the forefront of chemistry are efforts to catalytically transform the inert C-H bonds in alkanes to more useful products using metal compounds. The goal is to observe binding and cleavage of alkane C-H bonds on metals or to use related silane Si-H bonding as models, analogous to the discovery of hydrogen (H 2 ) binding to metals. Studies of these unique sigma complexes (M hor-ellipsis H-Y; Y double-bond H, Si, C) will aid in developing new catalysts or technologies relevant to DOE interest, e.g., new methods for tritium isotope separation. Several transition metals (Mo, W, Mn, and Pt) were found to reversibly bind and cleave H 2 , silanes, and halocarbons. The first metal-SiH 4 complexes, thus serving as a model for methane reactions. A second goal is to study the dynamics and energetics of H-Y bonds on metals by neutron scattering, and evidence for interactions between bound H-Y and nearby H atoms on metal complexes has been found

  8. Is Monte Carlo embarrassingly parallel?

    Energy Technology Data Exchange (ETDEWEB)

    Hoogenboom, J. E. [Delft Univ. of Technology, Mekelweg 15, 2629 JB Delft (Netherlands); Delft Nuclear Consultancy, IJsselzoom 2, 2902 LB Capelle aan den IJssel (Netherlands)

    2012-07-01

    Monte Carlo is often stated as being embarrassingly parallel. However, running a Monte Carlo calculation, especially a reactor criticality calculation, in parallel using tens of processors shows a serious limitation in speedup and the execution time may even increase beyond a certain number of processors. In this paper the main causes of the loss of efficiency when using many processors are analyzed using a simple Monte Carlo program for criticality. The basic mechanism for parallel execution is MPI. One of the bottlenecks turn out to be the rendez-vous points in the parallel calculation used for synchronization and exchange of data between processors. This happens at least at the end of each cycle for fission source generation in order to collect the full fission source distribution for the next cycle and to estimate the effective multiplication factor, which is not only part of the requested results, but also input to the next cycle for population control. Basic improvements to overcome this limitation are suggested and tested. Also other time losses in the parallel calculation are identified. Moreover, the threading mechanism, which allows the parallel execution of tasks based on shared memory using OpenMP, is analyzed in detail. Recommendations are given to get the maximum efficiency out of a parallel Monte Carlo calculation. (authors)

  9. Is Monte Carlo embarrassingly parallel?

    International Nuclear Information System (INIS)

    Hoogenboom, J. E.

    2012-01-01

    Monte Carlo is often stated as being embarrassingly parallel. However, running a Monte Carlo calculation, especially a reactor criticality calculation, in parallel using tens of processors shows a serious limitation in speedup and the execution time may even increase beyond a certain number of processors. In this paper the main causes of the loss of efficiency when using many processors are analyzed using a simple Monte Carlo program for criticality. The basic mechanism for parallel execution is MPI. One of the bottlenecks turn out to be the rendez-vous points in the parallel calculation used for synchronization and exchange of data between processors. This happens at least at the end of each cycle for fission source generation in order to collect the full fission source distribution for the next cycle and to estimate the effective multiplication factor, which is not only part of the requested results, but also input to the next cycle for population control. Basic improvements to overcome this limitation are suggested and tested. Also other time losses in the parallel calculation are identified. Moreover, the threading mechanism, which allows the parallel execution of tasks based on shared memory using OpenMP, is analyzed in detail. Recommendations are given to get the maximum efficiency out of a parallel Monte Carlo calculation. (authors)

  10. Exact Monte Carlo for molecules

    International Nuclear Information System (INIS)

    Lester, W.A. Jr.; Reynolds, P.J.

    1985-03-01

    A brief summary of the fixed-node quantum Monte Carlo method is presented. Results obtained for binding energies, the classical barrier height for H + H 2 , and the singlet-triplet splitting in methylene are presented and discussed. 17 refs

  11. Monte Carlo - Advances and Challenges

    International Nuclear Information System (INIS)

    Brown, Forrest B.; Mosteller, Russell D.; Martin, William R.

    2008-01-01

    Abstract only, full text follows: With ever-faster computers and mature Monte Carlo production codes, there has been tremendous growth in the application of Monte Carlo methods to the analysis of reactor physics and reactor systems. In the past, Monte Carlo methods were used primarily for calculating k eff of a critical system. More recently, Monte Carlo methods have been increasingly used for determining reactor power distributions and many design parameters, such as β eff , l eff , τ, reactivity coefficients, Doppler defect, dominance ratio, etc. These advanced applications of Monte Carlo methods are now becoming common, not just feasible, but bring new challenges to both developers and users: Convergence of 3D power distributions must be assured; confidence interval bias must be eliminated; iterated fission probabilities are required, rather than single-generation probabilities; temperature effects including Doppler and feedback must be represented; isotopic depletion and fission product buildup must be modeled. This workshop focuses on recent advances in Monte Carlo methods and their application to reactor physics problems, and on the resulting challenges faced by code developers and users. The workshop is partly tutorial, partly a review of the current state-of-the-art, and partly a discussion of future work that is needed. It should benefit both novice and expert Monte Carlo developers and users. In each of the topic areas, we provide an overview of needs, perspective on past and current methods, a review of recent work, and discussion of further research and capabilities that are required. Electronic copies of all workshop presentations and material will be available. The workshop is structured as 2 morning and 2 afternoon segments: - Criticality Calculations I - convergence diagnostics, acceleration methods, confidence intervals, and the iterated fission probability, - Criticality Calculations II - reactor kinetics parameters, dominance ratio, temperature

  12. Light-Induced C-H Arylation of (Hetero)arenes by In Situ Generated Diazo Anhydrides.

    Science.gov (United States)

    Cantillo, David; Mateos, Carlos; Rincon, Juan A; de Frutos, Oscar; Kappe, C Oliver

    2015-09-07

    Diazo anhydrides (Ar-N=N-O-N=N-Ar) have been known since 1896 but have rarely been used in synthesis. This communication describes the development of a photochemical catalyst-free C-H arylation methodology for the preparation of bi(hetero)aryls by the one-pot reaction of anilines with tert-butyl nitrite and (hetero)arenes under neutral conditions. The key step in this procedure is the in situ formation and subsequent photochemical (>300 nm) homolytic cleavage of a transient diazo anhydride intermediate. The generated aryl radical then efficiently reacts with a (hetero)arene to form the desired bi(hetero)aryls producing only nitrogen, water, and tert-butanol as byproducts. The scope of the reaction for several substituted anilines and (hetero)arenes was investigated. A continuous-flow protocol increasing selectivity and safety has been developed enabling the experimentally straightforward preparation of a variety of substituted bi(hetero)aryls within 45 min of reaction time. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Improved modification for the density-functional theory calculation of thermodynamic properties for C-H-O composite compounds.

    Science.gov (United States)

    Liu, Min Hsien; Chen, Cheng; Hong, Yaw Shun

    2005-02-08

    A three-parametric modification equation and the least-squares approach are adopted to calibrating hybrid density-functional theory energies of C(1)-C(10) straight-chain aldehydes, alcohols, and alkoxides to accurate enthalpies of formation DeltaH(f) and Gibbs free energies of formation DeltaG(f), respectively. All calculated energies of the C-H-O composite compounds were obtained based on B3LYP6-311++G(3df,2pd) single-point energies and the related thermal corrections of B3LYP6-31G(d,p) optimized geometries. This investigation revealed that all compounds had 0.05% average absolute relative error (ARE) for the atomization energies, with mean value of absolute error (MAE) of just 2.1 kJ/mol (0.5 kcal/mol) for the DeltaH(f) and 2.4 kJ/mol (0.6 kcal/mol) for the DeltaG(f) of formation.

  14. Durability-enhanced two-dimensional hole gas of C-H diamond surface for complementary power inverter applications.

    Science.gov (United States)

    Kawarada, Hiroshi; Yamada, Tetsuya; Xu, Dechen; Tsuboi, Hidetoshi; Kitabayashi, Yuya; Matsumura, Daisuke; Shibata, Masanobu; Kudo, Takuya; Inaba, Masafumi; Hiraiwa, Atsushi

    2017-02-20

    Complementary power field effect transistors (FETs) based on wide bandgap materials not only provide high-voltage switching capability with the reduction of on-resistance and switching losses, but also enable a smart inverter system by the dramatic simplification of external circuits. However, p-channel power FETs with equivalent performance to those of n-channel FETs are not obtained in any wide bandgap material other than diamond. Here we show that a breakdown voltage of more than 1600 V has been obtained in a diamond metal-oxide-semiconductor (MOS) FET with a p-channel based on a two-dimensional hole gas (2DHG). Atomic layer deposited (ALD) Al 2 O 3 induces the 2DHG ubiquitously on a hydrogen-terminated (C-H) diamond surface and also acts as both gate insulator and passivation layer. The high voltage performance is equivalent to that of state-of-the-art SiC planar n-channel FETs and AlGaN/GaN FETs. The drain current density in the on-state is also comparable to that of these two FETs with similar device size and V B .

  15. Surface morphology and grain analysis of successively industrially grown amorphous hydrogenated carbon films (a-C:H) on silicon

    Science.gov (United States)

    Catena, Alberto; McJunkin, Thomas; Agnello, Simonpietro; Gelardi, Franco M.; Wehner, Stefan; Fischer, Christian B.

    2015-08-01

    Silicon (1 0 0) has been gradually covered by amorphous hydrogenated carbon (a-C:H) films via an industrial process. Two types of these diamond-like carbon (DLC) coatings, one more flexible (f-DLC) and one more robust (r-DLC), have been investigated. Both types have been grown by a radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique with acetylene plasma. Surface morphologies have been studied in detail by atomic force microscopy (AFM) and Raman spectroscopy has been used to investigate the DLC structure. Both types appeared to have very similar morphology and sp2 carbon arrangement. The average height and area for single grains have been analyzed for all depositions. A random distribution of grain heights was found for both types. The individual grain structures between the f- and r-type revealed differences: the shape for the f-DLC grains is steeper than for the r-DLC grains. By correlating the average grain heights to the average grain areas for all depositions a limited region is identified, suggesting a certain regularity during the DLC deposition mechanisms that confines both values. A growth of the sp2 carbon entities for high r-DLC depositions is revealed and connected to a structural rearrangement of carbon atom hybridizations and hydrogen content in the DLC structure.

  16. Histone HIST1H1C/H1.2 regulates autophagy in the development of diabetic retinopathy.

    Science.gov (United States)

    Wang, Wenjun; Wang, Qing; Wan, Danyang; Sun, Yue; Wang, Lin; Chen, Hong; Liu, Chengyu; Petersen, Robert B; Li, Jianshuang; Xue, Weili; Zheng, Ling; Huang, Kun

    2017-05-04

    Autophagy plays critical and complex roles in many human diseases, including diabetes and its complications. However, the role of autophagy in the development of diabetic retinopathy remains uncertain. Core histone modifications have been reported involved in the development of diabetic retinopathy, but little is known about the histone variants. Here, we observed increased autophagy and histone HIST1H1C/H1.2, an important variant of the linker histone H1, in the retinas of type 1 diabetic rodents. Overexpression of histone HIST1H1C upregulates SIRT1 and HDAC1 to maintain the deacetylation status of H4K16, leads to upregulation of ATG proteins, then promotes autophagy in cultured retinal cell line. Histone HIST1H1C overexpression also promotes inflammation and cell toxicity in vitro. Knockdown of histone HIST1H1C reduces both the basal and stresses (including high glucose)-induced autophagy, and inhibits high glucose induced inflammation and cell toxicity. Importantly, AAV-mediated histone HIST1H1C overexpression in the retinas leads to increased autophagy, inflammation, glial activation and neuron loss, similar to the pathological changes identified in the early stage of diabetic retinopathy. Furthermore, knockdown of histone Hist1h1c by siRNA in the retinas of diabetic mice significantly attenuated the diabetes-induced autophagy, inflammation, glial activation and neuron loss. These results indicate that histone HIST1H1C may offer a novel therapeutic target for preventing diabetic retinopathy.

  17. Pd-Catalyzed Consecutive C-H Arylation Triggered Cyclotrimerization: Synthesis of Star-shaped Benzotristhiazoles and Benzotrisoxazoles.

    Science.gov (United States)

    Xu, Zhanqiang; Oniwa, Kazuaki; Kikuchi, Hiromasa; Bao, Ming; Yamamoto, Yoshinori; Jin, Tienan; Terada, Masahiro

    2018-05-18

    Star-shaped π-extended molecules comprising discotic aromatic cores and peripheral π-conjugated arms have attracted significant attention as diverse optoelectronic materials in terms of their large π-surface, tunable self-assembly, enhanced charge transport and fluorescence, and liquid crystallinity. Although many efforts have been made in construction of various aromatic discotic cores, a new class of C3-symmetric star-shaped discotic π-molecules consisting of electron-deficient benzotristhiazole and benzotrisoxazole cores remains unexplored owing to the unachievable synthetic approaches, which are expected to exhibit distinct optoelectronic properties. Herein, we report a novel and highly efficient Pd-catalyzed cyclotrimerization of the functionalized thiazoles or oxazoles for the construction of a new class of discotic molecules of benzotristhiazole and benzotrisoxazole central cores with star-shaped π-conjugated arms. The combination of Pd2(dba)3/XPhos catalyst systems with the 4-bromo-substituted thiazole enables the formation of a sufficiently stable thiazole-Pd species that participates in the subsequent C-H arylations consecutively to form the corresponding cyclic trimer products. This new class of star-shaped discotic π-extended products showed tunable energy levels and high fluorescence quantum yields that make them promising candidates in optoelectronic application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence.

    Science.gov (United States)

    Ikemoto, Hideya; Yoshino, Tatsuhiko; Sakata, Ken; Matsunaga, Shigeki; Kanai, Motomu

    2014-04-09

    A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.

  19. Romanian government bond market

    Directory of Open Access Journals (Sweden)

    Cornelia POP

    2012-12-01

    Full Text Available The present paper aims to present the level of development reached by Romanian government bond market segment, as part of the country financial market. The analysis will be descriptive (the data series available for Romania are short, based on the secondary data offered by the official bodies involved in the process of issuing and trading the Romanian government bonds (Romanian Ministry of Public Finance, Romanian National Bank and Bucharest Stock Exchange, and also on secondary data provided by the Federation of European Stock Exchanges.To enhance the market credibility as a benchmark, a various combination of measures is necessary; among these measures are mentioned: the extension of the yield curve; the issuance calendars in order to improve transparency; increasing the disclosure of information on public debt issuance and statistics; holding regular meetings with dealers, institutional investors and rating agencies; introducing a system of primary dealers; establishing a repurchase (repo market in the government bond market. These measures will be discussed based on the evolution presented inside the paper.The paper conclude with the fact that, until now, the Romanian government bond market did not provide a benchmark for the domestic financial market and that further efforts are needed in order to increase the government bond market transparency and liquidity.

  20. Interstellar hydrogen bonding

    Science.gov (United States)

    Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

    2018-06-01

    This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

  1. Safe and Liquid Mortgage Bonds

    DEFF Research Database (Denmark)

    Dick-Nielsen, Jens; Gyntelberg, Jacob; Lund, Jesper

    This paper shows that strict match pass-through funding of covered bonds provides safe and liquid mortgage bonds. Despite a 30% drop in house prices during the 2008 global crisis Danish mortgage bonds remained as liquid as most European government bonds. The Danish pass-through system effectively...... eliminates credit risk from the investor's perspective. Similar to other safe bonds, funding liquidity becomes the main driver of mortgage bond liquidity and this creates commonality in liquidity across markets and countries. These findings have implications for how to design a robust mortgage bond system...

  2. C-H and C-C activation of n -butane with zirconium hydrides supported on SBA15 containing N-donor ligands: [(≡SiNH-)(≡SiX-)ZrH2], [(≡SiNH-)(≡SiX-)2ZrH], and[(≡SiN=)(≡SiX-)ZrH] (X = -NH-, -O-). A DFT study

    KAUST Repository

    Pasha, Farhan Ahmad; Bendjeriou-Sedjerari, Anissa; Huang, Kuo-Wei; Basset, Jean-Marie

    2014-01-01

    : [(≡SiNH-)(≡SiO-)ZrH2] (A), [(≡SiNH-)2ZrH2] (B), [(≡SiNH-)(≡SiO-) 2ZrH] (C), [(≡SiNH-)2(≡SiO-)ZrH] (D), [(≡SiN=)(≡Si-O-)ZrH] (E), and [(≡SiN=)(≡SiNH-)ZrH] (F). The roles of these hydrides have been investigated in C-H/C-C bond activation and cleavage

  3. (U) Introduction to Monte Carlo Methods

    Energy Technology Data Exchange (ETDEWEB)

    Hungerford, Aimee L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-03-20

    Monte Carlo methods are very valuable for representing solutions to particle transport problems. Here we describe a “cook book” approach to handling the terms in a transport equation using Monte Carlo methods. Focus is on the mechanics of a numerical Monte Carlo code, rather than the mathematical foundations of the method.

  4. Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

    Science.gov (United States)

    Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

    2017-09-28

    High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

  5. Quantum Monte Carlo: Faster, More Reliable, And More Accurate

    Science.gov (United States)

    Anderson, Amos Gerald

    2010-06-01

    The Schrodinger Equation has been available for about 83 years, but today, we still strain to apply it accurately to molecules of interest. The difficulty is not theoretical in nature, but practical, since we're held back by lack of sufficient computing power. Consequently, effort is applied to find acceptable approximations to facilitate real time solutions. In the meantime, computer technology has begun rapidly advancing and changing the way we think about efficient algorithms. For those who can reorganize their formulas to take advantage of these changes and thereby lift some approximations, incredible new opportunities await. Over the last decade, we've seen the emergence of a new kind of computer processor, the graphics card. Designed to accelerate computer games by optimizing quantity instead of quality in processor, they have become of sufficient quality to be useful to some scientists. In this thesis, we explore the first known use of a graphics card to computational chemistry by rewriting our Quantum Monte Carlo software into the requisite "data parallel" formalism. We find that notwithstanding precision considerations, we are able to speed up our software by about a factor of 6. The success of a Quantum Monte Carlo calculation depends on more than just processing power. It also requires the scientist to carefully design the trial wavefunction used to guide simulated electrons. We have studied the use of Generalized Valence Bond wavefunctions to simply, and yet effectively, captured the essential static correlation in atoms and molecules. Furthermore, we have developed significantly improved two particle correlation functions, designed with both flexibility and simplicity considerations, representing an effective and reliable way to add the necessary dynamic correlation. Lastly, we present our method for stabilizing the statistical nature of the calculation, by manipulating configuration weights, thus facilitating efficient and robust calculations. Our

  6. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting

    2015-01-01

    This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

  7. Continuing bonds and place.

    Science.gov (United States)

    Jonsson, Annika; Walter, Tony

    2017-08-01

    Where do people feel closest to those they have lost? This article explores how continuing bonds with a deceased person can be rooted in a particular place or places. Some conceptual resources are sketched, namely continuing bonds, place attachment, ancestral places, home, reminder theory, and loss of place. The authors use these concepts to analyze interview material with seven Swedes and five Britons who often thought warmly of the deceased as residing in a particular place and often performing characteristic actions. The destruction of such a place, by contrast, could create a troubling, haunting absence, complicating the deceased's absent-presence.

  8. Interexaminer reliability in clinical measurement of L*C*h* values of anterior teeth using a spectrophotometer.

    Science.gov (United States)

    Hassel, Alexander J; Grossmann, Anne-christiane; Schmitter, Marc; Balke, Zibandeh; Buzello, Anja M

    2007-01-01

    The objective of this study was to investigate interexaminer reliability in the clinical measurement of the L*C*h* (lightness/value, chroma, hue) values of anterior teeth using a spectrophotometer (Vita Easyshade). The basic color of the maxillary right central incisors and canines of 23 subjects was spectrophotometrically determined by 4 clinicians and an experienced user (development manager) of the spectrophotometer. Also, to analyze the effect of different training with the instrument on interexaminer reliability, 2 of the clinicians were instructed in the use of the spectrophotometer by the experienced examiner, whereas the others instructed themselves by studying the operating manual. Agreement between all examiners was acceptable to excellent (intraclass coefficient > 0.4). The mean value of the measured differences for the central incisors of all subjects for L* values was 5 (for C* = 3.8, h* = 2.7 degrees) and for canines, the mean L* was 4.5 (C* = 3, h* = 1.6 degrees). Results from comparison of the 2 different training methods were inconsistent. Agreement with the experienced examiner ranged from not acceptable (C* values for incisors of self-instructed examiners) to excellent. The distribution of the measurements of 1 subject could lead to deviations in color, probably with clinical impact. For canines, the measurements were at least equally reproducible (in some cases significantly more reproducible) compared to central incisors. Because of the small number of examiners and the inconsistent results, it was not possible to reach a definite conclusion about the effect of different training methods on interexaminer reliability.

  9. 13C ENDOR Spectroscopy of Lipoxygenase-Substrate Complexes Reveals the Structural Basis for C-H Activation by Tunneling.

    Science.gov (United States)

    Horitani, Masaki; Offenbacher, Adam R; Carr, Cody A Marcus; Yu, Tao; Hoeke, Veronika; Cutsail, George E; Hammes-Schiffer, Sharon; Klinman, Judith P; Hoffman, Brian M

    2017-02-08

    In enzymatic C-H activation by hydrogen tunneling, reduced barrier width is important for efficient hydrogen wave function overlap during catalysis. For native enzymes displaying nonadiabatic tunneling, the dominant reactive hydrogen donor-acceptor distance (DAD) is typically ca. 2.7 Å, considerably shorter than normal van der Waals distances. Without a ground state substrate-bound structure for the prototypical nonadiabatic tunneling system, soybean lipoxygenase (SLO), it has remained unclear whether the requisite close tunneling distance occurs through an unusual ground state active site arrangement or by thermally sampling conformational substates. Herein, we introduce Mn 2+ as a spin-probe surrogate for the SLO Fe ion; X-ray diffraction shows Mn-SLO is structurally faithful to the native enzyme. 13 C ENDOR then reveals the locations of 13 C10 and reactive 13 C11 of linoleic acid relative to the metal; 1 H ENDOR and molecular dynamics simulations of the fully solvated SLO model using ENDOR-derived restraints give additional metrical information. The resulting three-dimensional representation of the SLO active site ground state contains a reactive (a) conformer with hydrogen DAD of ∼3.1 Å, approximately van der Waals contact, plus an inactive (b) conformer with even longer DAD, establishing that stochastic conformational sampling is required to achieve reactive tunneling geometries. Tunneling-impaired SLO variants show increased DADs and variations in substrate positioning and rigidity, confirming previous kinetic and theoretical predictions of such behavior. Overall, this investigation highlights the (i) predictive power of nonadiabatic quantum treatments of proton-coupled electron transfer in SLO and (ii) sensitivity of ENDOR probes to test, detect, and corroborate kinetically predicted trends in active site reactivity and to reveal unexpected features of active site architecture.

  10. Isotopic depletion with Monte Carlo

    International Nuclear Information System (INIS)

    Martin, W.R.; Rathkopf, J.A.

    1996-06-01

    This work considers a method to deplete isotopes during a time- dependent Monte Carlo simulation of an evolving system. The method is based on explicitly combining a conventional estimator for the scalar flux with the analytical solutions to the isotopic depletion equations. There are no auxiliary calculations; the method is an integral part of the Monte Carlo calculation. The method eliminates negative densities and reduces the variance in the estimates for the isotope densities, compared to existing methods. Moreover, existing methods are shown to be special cases of the general method described in this work, as they can be derived by combining a high variance estimator for the scalar flux with a low-order approximation to the analytical solution to the depletion equation

  11. Monte Carlo Methods in ICF

    Science.gov (United States)

    Zimmerman, George B.

    Monte Carlo methods appropriate to simulate the transport of x-rays, neutrons, ions and electrons in Inertial Confinement Fusion targets are described and analyzed. The Implicit Monte Carlo method of x-ray transport handles symmetry within indirect drive ICF hohlraums well, but can be improved 50X in efficiency by angular biasing the x-rays towards the fuel capsule. Accurate simulation of thermonuclear burn and burn diagnostics involves detailed particle source spectra, charged particle ranges, inflight reaction kinematics, corrections for bulk and thermal Doppler effects and variance reduction to obtain adequate statistics for rare events. It is found that the effects of angular Coulomb scattering must be included in models of charged particle transport through heterogeneous materials.

  12. Monte Carlo methods in ICF

    International Nuclear Information System (INIS)

    Zimmerman, G.B.

    1997-01-01

    Monte Carlo methods appropriate to simulate the transport of x-rays, neutrons, ions and electrons in Inertial Confinement Fusion targets are described and analyzed. The Implicit Monte Carlo method of x-ray transport handles symmetry within indirect drive ICF hohlraums well, but can be improved 50X in efficiency by angular biasing the x-rays towards the fuel capsule. Accurate simulation of thermonuclear burn and burn diagnostics involves detailed particle source spectra, charged particle ranges, inflight reaction kinematics, corrections for bulk and thermal Doppler effects and variance reduction to obtain adequate statistics for rare events. It is found that the effects of angular Coulomb scattering must be included in models of charged particle transport through heterogeneous materials. copyright 1997 American Institute of Physics

  13. Monte Carlo methods in ICF

    International Nuclear Information System (INIS)

    Zimmerman, George B.

    1997-01-01

    Monte Carlo methods appropriate to simulate the transport of x-rays, neutrons, ions and electrons in Inertial Confinement Fusion targets are described and analyzed. The Implicit Monte Carlo method of x-ray transport handles symmetry within indirect drive ICF hohlraums well, but can be improved 50X in efficiency by angular biasing the x-rays towards the fuel capsule. Accurate simulation of thermonuclear burn and burn diagnostics involves detailed particle source spectra, charged particle ranges, inflight reaction kinematics, corrections for bulk and thermal Doppler effects and variance reduction to obtain adequate statistics for rare events. It is found that the effects of angular Coulomb scattering must be included in models of charged particle transport through heterogeneous materials

  14. Shell model Monte Carlo methods

    International Nuclear Information System (INIS)

    Koonin, S.E.; Dean, D.J.; Langanke, K.

    1997-01-01

    We review quantum Monte Carlo methods for dealing with large shell model problems. These methods reduce the imaginary-time many-body evolution operator to a coherent superposition of one-body evolutions in fluctuating one-body fields; the resultant path integral is evaluated stochastically. We first discuss the motivation, formalism, and implementation of such Shell Model Monte Carlo (SMMC) methods. There then follows a sampler of results and insights obtained from a number of applications. These include the ground state and thermal properties of pf-shell nuclei, the thermal and rotational behavior of rare-earth and γ-soft nuclei, and the calculation of double beta-decay matrix elements. Finally, prospects for further progress in such calculations are discussed. (orig.)

  15. A contribution Monte Carlo method

    International Nuclear Information System (INIS)

    Aboughantous, C.H.

    1994-01-01

    A Contribution Monte Carlo method is developed and successfully applied to a sample deep-penetration shielding problem. The random walk is simulated in most of its parts as in conventional Monte Carlo methods. The probability density functions (pdf's) are expressed in terms of spherical harmonics and are continuous functions in direction cosine and azimuthal angle variables as well as in position coordinates; the energy is discretized in the multigroup approximation. The transport pdf is an unusual exponential kernel strongly dependent on the incident and emergent directions and energies and on the position of the collision site. The method produces the same results obtained with the deterministic method with a very small standard deviation, with as little as 1,000 Contribution particles in both analog and nonabsorption biasing modes and with only a few minutes CPU time

  16. Shell model Monte Carlo methods

    International Nuclear Information System (INIS)

    Koonin, S.E.

    1996-01-01

    We review quantum Monte Carlo methods for dealing with large shell model problems. These methods reduce the imaginary-time many-body evolution operator to a coherent superposition of one-body evolutions in fluctuating one-body fields; resultant path integral is evaluated stochastically. We first discuss the motivation, formalism, and implementation of such Shell Model Monte Carlo methods. There then follows a sampler of results and insights obtained from a number of applications. These include the ground state and thermal properties of pf-shell nuclei, thermal behavior of γ-soft nuclei, and calculation of double beta-decay matrix elements. Finally, prospects for further progress in such calculations are discussed. 87 refs

  17. Parallel Monte Carlo reactor neutronics

    International Nuclear Information System (INIS)

    Blomquist, R.N.; Brown, F.B.

    1994-01-01

    The issues affecting implementation of parallel algorithms for large-scale engineering Monte Carlo neutron transport simulations are discussed. For nuclear reactor calculations, these include load balancing, recoding effort, reproducibility, domain decomposition techniques, I/O minimization, and strategies for different parallel architectures. Two codes were parallelized and tested for performance. The architectures employed include SIMD, MIMD-distributed memory, and workstation network with uneven interactive load. Speedups linear with the number of nodes were achieved

  18. Elements of Monte Carlo techniques

    International Nuclear Information System (INIS)

    Nagarajan, P.S.

    2000-01-01

    The Monte Carlo method is essentially mimicking the real world physical processes at the microscopic level. With the incredible increase in computing speeds and ever decreasing computing costs, there is widespread use of the method for practical problems. The method is used in calculating algorithm-generated sequences known as pseudo random sequence (prs)., probability density function (pdf), test for randomness, extension to multidimensional integration etc

  19. Adaptive Multilevel Monte Carlo Simulation

    KAUST Repository

    Hoel, H

    2011-08-23

    This work generalizes a multilevel forward Euler Monte Carlo method introduced in Michael B. Giles. (Michael Giles. Oper. Res. 56(3):607–617, 2008.) for the approximation of expected values depending on the solution to an Itô stochastic differential equation. The work (Michael Giles. Oper. Res. 56(3):607– 617, 2008.) proposed and analyzed a forward Euler multilevelMonte Carlo method based on a hierarchy of uniform time discretizations and control variates to reduce the computational effort required by a standard, single level, Forward Euler Monte Carlo method. This work introduces an adaptive hierarchy of non uniform time discretizations, generated by an adaptive algorithmintroduced in (AnnaDzougoutov et al. Raùl Tempone. Adaptive Monte Carlo algorithms for stopped diffusion. In Multiscale methods in science and engineering, volume 44 of Lect. Notes Comput. Sci. Eng., pages 59–88. Springer, Berlin, 2005; Kyoung-Sook Moon et al. Stoch. Anal. Appl. 23(3):511–558, 2005; Kyoung-Sook Moon et al. An adaptive algorithm for ordinary, stochastic and partial differential equations. In Recent advances in adaptive computation, volume 383 of Contemp. Math., pages 325–343. Amer. Math. Soc., Providence, RI, 2005.). This form of the adaptive algorithm generates stochastic, path dependent, time steps and is based on a posteriori error expansions first developed in (Anders Szepessy et al. Comm. Pure Appl. Math. 54(10):1169– 1214, 2001). Our numerical results for a stopped diffusion problem, exhibit savings in the computational cost to achieve an accuracy of ϑ(TOL),from(TOL−3), from using a single level version of the adaptive algorithm to ϑ(((TOL−1)log(TOL))2).

  20. Geometrical splitting in Monte Carlo

    International Nuclear Information System (INIS)

    Dubi, A.; Elperin, T.; Dudziak, D.J.

    1982-01-01

    A statistical model is presented by which a direct statistical approach yielded an analytic expression for the second moment, the variance ratio, and the benefit function in a model of an n surface-splitting Monte Carlo game. In addition to the insight into the dependence of the second moment on the splitting parameters the main importance of the expressions developed lies in their potential to become a basis for in-code optimization of splitting through a general algorithm. Refs

  1. Extending canonical Monte Carlo methods

    International Nuclear Information System (INIS)

    Velazquez, L; Curilef, S

    2010-01-01

    In this paper, we discuss the implications of a recently obtained equilibrium fluctuation-dissipation relation for the extension of the available Monte Carlo methods on the basis of the consideration of the Gibbs canonical ensemble to account for the existence of an anomalous regime with negative heat capacities C α with α≈0.2 for the particular case of the 2D ten-state Potts model

  2. Non statistical Monte-Carlo

    International Nuclear Information System (INIS)

    Mercier, B.

    1985-04-01

    We have shown that the transport equation can be solved with particles, like the Monte-Carlo method, but without random numbers. In the Monte-Carlo method, particles are created from the source, and are followed from collision to collision until either they are absorbed or they leave the spatial domain. In our method, particles are created from the original source, with a variable weight taking into account both collision and absorption. These particles are followed until they leave the spatial domain, and we use them to determine a first collision source. Another set of particles is then created from this first collision source, and tracked to determine a second collision source, and so on. This process introduces an approximation which does not exist in the Monte-Carlo method. However, we have analyzed the effect of this approximation, and shown that it can be limited. Our method is deterministic, gives reproducible results. Furthermore, when extra accuracy is needed in some region, it is easier to get more particles to go there. It has the same kind of applications: rather problems where streaming is dominant than collision dominated problems

  3. BREM5 electroweak Monte Carlo

    International Nuclear Information System (INIS)

    Kennedy, D.C. II.

    1987-01-01

    This is an update on the progress of the BREMMUS Monte Carlo simulator, particularly in its current incarnation, BREM5. The present report is intended only as a follow-up to the Mark II/Granlibakken proceedings, and those proceedings should be consulted for a complete description of the capabilities and goals of the BREMMUS program. The new BREM5 program improves on the previous version of BREMMUS, BREM2, in a number of important ways. In BREM2, the internal loop (oblique) corrections were not treated in consistent fashion, a deficiency that led to renormalization scheme-dependence; i.e., physical results, such as cross sections, were dependent on the method used to eliminate infinities from the theory. Of course, this problem cannot be tolerated in a Monte Carlo designed for experimental use. BREM5 incorporates a new way of treating the oblique corrections, as explained in the Granlibakken proceedings, that guarantees renormalization scheme-independence and dramatically simplifies the organization and calculation of radiative corrections. This technique is to be presented in full detail in a forthcoming paper. BREM5 is, at this point, the only Monte Carlo to contain the entire set of one-loop corrections to electroweak four-fermion processes and renormalization scheme-independence. 3 figures

  4. Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization.

    Science.gov (United States)

    Tsai, Hung-Chang; Huang, Yen-Hsiang; Chou, Chih-Ming

    2018-03-02

    A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.

  5. Statistical implications in Monte Carlo depletions - 051

    International Nuclear Information System (INIS)

    Zhiwen, Xu; Rhodes, J.; Smith, K.

    2010-01-01

    As a result of steady advances of computer power, continuous-energy Monte Carlo depletion analysis is attracting considerable attention for reactor burnup calculations. The typical Monte Carlo analysis is set up as a combination of a Monte Carlo neutron transport solver and a fuel burnup solver. Note that the burnup solver is a deterministic module. The statistical errors in Monte Carlo solutions are introduced into nuclide number densities and propagated along fuel burnup. This paper is towards the understanding of the statistical implications in Monte Carlo depletions, including both statistical bias and statistical variations in depleted fuel number densities. The deterministic Studsvik lattice physics code, CASMO-5, is modified to model the Monte Carlo depletion. The statistical bias in depleted number densities is found to be negligible compared to its statistical variations, which, in turn, demonstrates the correctness of the Monte Carlo depletion method. Meanwhile, the statistical variation in number densities generally increases with burnup. Several possible ways of reducing the statistical errors are discussed: 1) to increase the number of individual Monte Carlo histories; 2) to increase the number of time steps; 3) to run additional independent Monte Carlo depletion cases. Finally, a new Monte Carlo depletion methodology, called the batch depletion method, is proposed, which consists of performing a set of independent Monte Carlo depletions and is thus capable of estimating the overall statistical errors including both the local statistical error and the propagated statistical error. (authors)

  6. Local atomic structure and chemical order in amorphous SiGe:H and SiC:H alloys

    International Nuclear Information System (INIS)

    Pisarkiewicz, T.; Stapinski, T.

    1994-01-01

    The local structure and chemical ordering in amorphous hydrogenated silicon-germanium and silicon-carbon alloys were analyzed mainly with the help of extended x-ray absorption fine structure (EXAFS) spectroscopy, Raman scattering and electron diffraction. Ge-Ge and Ge-Si distances were found to be independent of concentration and the composition of the first coordination shell around Ge is consistent with a random mixing of the two species in a-Si 1-x Ge:H alloy. The first-coordination-shell average bond lengths for Si-Si and SiC in a-Si 1-x C x :H are also constant with concentration x and the comparison of the first coordination shell composition around Si with average concentration indicates that the alloys tends to be chemically ordered. The degree of crystallinity in microcrystalline Si films determined by EXAFS is in agreement with that obtained in Raman scattering analysis. (author). 16 refs, 5 figs

  7. Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

    Science.gov (United States)

    Wang, He; Tang, Guodong; Li, Xingwei

    2015-10-26

    Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Engineering an improved IgG4 molecule with reduced disulfide bond heterogeneity and increased Fab domain thermal stability.

    Science.gov (United States)

    Peters, Shirley J; Smales, C Mark; Henry, Alistair J; Stephens, Paul E; West, Shauna; Humphreys, David P

    2012-07-13

    The integrity of antibody structure, stability, and biophysical characterization are becoming increasingly important as antibodies receive increasing scrutiny from regulatory authorities. We altered the disulfide bond arrangement of an IgG4 molecule by mutation of the Cys at the N terminus of the heavy chain constant domain 1 (C(H)1) (Kabat position 127) to a Ser and introduction of a Cys at a variety of positions (positions 227-230) at the C terminus of C(H)1. An inter-LC-C(H)1 disulfide bond is thus formed, which mimics the disulfide bond arrangement found in an IgG1 molecule. The antibody species present in the supernatant following transient expression in Chinese hamster ovary cells were analyzed by immunoblot to investigate product homogeneity, and purified product was analyzed by a thermofluor assay to determine thermal stability. We show that the light chain can form an inter-LC-C(H)1 disulfide bond with a Cys when present at several positions on the upper hinge (positions 227-230) and that such engineered disulfide bonds can consequently increase the Fab domain thermal stability between 3 and 6.8 °C. The IgG4 disulfide mutants displaying the greatest increase in Fab thermal stability were also the most homogeneous in terms of disulfide bond arrangement and antibody species present. Importantly, mutations did not affect the affinity for antigen of the resultant molecules. In combination with the previously described S241P mutation, we present an IgG4 molecule with increased Fab thermal stability and reduced product heterogeneity that potentially offers advantages for the production of IgG4 molecules.

  9. Integration of European Bond Markets

    DEFF Research Database (Denmark)

    Christiansen, Charlotte

    2014-01-01

    I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non-EMU memb......I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non...

  10. Amalgam shear bond strength to dentin using different bonding agents.

    Science.gov (United States)

    Vargas, M A; Denehy, G E; Ratananakin, T

    1994-01-01

    This study evaluated the shear bond strength of amalgam to dentin using five different bonding agents: Amalgambond Plus, Optibond, Imperva Dual, All-Bond 2, and Clearfil Liner Bond. Flat dentin surfaces obtained by grinding the occlusal portion of 50 human third molars were used for this study. To contain the amalgam on the tooth surface, cylindrical plastic molds were placed on the dentin and secured with sticky wax. The bonding agents were then applied according to the manufacturers' instructions or light activated and Tytin amalgam was condensed into the plastic molds. The samples were thermocycled and shear bond strengths were determined using an Instron Universal Testing Machine. Analysis by one-way ANOVA indicated significant difference between the five groups (P < 0.05). The bond strength of amalgam to dentin was significantly higher with Amalgambond Plus using the High-Performance Additive than with the other four bonding agents.

  11. Multi-level quantum monte Carlo wave functions for complex reactions: The decomposition of α-hydroxy-dimethylnitrosamine

    NARCIS (Netherlands)

    Fracchia, F.; Filippi, Claudia; Amovilli, C.

    2014-01-01

    We present here several novel features of our recently proposed Jastrow linear generalized valence bond (J-LGVB) wave functions, which allow a consistently accurate description of complex potential energy surfaces (PES) of medium-large systems within quantum Monte Carlo (QMC). In particular, we

  12. Convertible bond valuation focusing on Chinese convertible bond market

    OpenAIRE

    Yang, Ke

    2010-01-01

    This paper mainly discusses the methods of valuation of convertible bonds in Chinese market. Different from common convertible bonds in European market, considering the complicate features of Chinese convertible bond, this paper represents specific pricing approaches for pricing convertible bonds with different provisions along with the increment of complexity of these provisions. More specifically, this paper represents the decomposing method and binomial tree method for pricing both of Non-...

  13. Monte Carlo simulations of lattice models for single polymer systems

    Science.gov (United States)

    Hsu, Hsiao-Ping

    2014-10-01

    Single linear polymer chains in dilute solutions under good solvent conditions are studied by Monte Carlo simulations with the pruned-enriched Rosenbluth method up to the chain length N ˜ O(10^4). Based on the standard simple cubic lattice model (SCLM) with fixed bond length and the bond fluctuation model (BFM) with bond lengths in a range between 2 and sqrt{10}, we investigate the conformations of polymer chains described by self-avoiding walks on the simple cubic lattice, and by random walks and non-reversible random walks in the absence of excluded volume interactions. In addition to flexible chains, we also extend our study to semiflexible chains for different stiffness controlled by a bending potential. The persistence lengths of chains extracted from the orientational correlations are estimated for all cases. We show that chains based on the BFM are more flexible than those based on the SCLM for a fixed bending energy. The microscopic differences between these two lattice models are discussed and the theoretical predictions of scaling laws given in the literature are checked and verified. Our simulations clarify that a different mapping ratio between the coarse-grained models and the atomistically realistic description of polymers is required in a coarse-graining approach due to the different crossovers to the asymptotic behavior.

  14. Monte Carlo simulations of lattice models for single polymer systems

    International Nuclear Information System (INIS)

    Hsu, Hsiao-Ping

    2014-01-01

    Single linear polymer chains in dilute solutions under good solvent conditions are studied by Monte Carlo simulations with the pruned-enriched Rosenbluth method up to the chain length N∼O(10 4 ). Based on the standard simple cubic lattice model (SCLM) with fixed bond length and the bond fluctuation model (BFM) with bond lengths in a range between 2 and √(10), we investigate the conformations of polymer chains described by self-avoiding walks on the simple cubic lattice, and by random walks and non-reversible random walks in the absence of excluded volume interactions. In addition to flexible chains, we also extend our study to semiflexible chains for different stiffness controlled by a bending potential. The persistence lengths of chains extracted from the orientational correlations are estimated for all cases. We show that chains based on the BFM are more flexible than those based on the SCLM for a fixed bending energy. The microscopic differences between these two lattice models are discussed and the theoretical predictions of scaling laws given in the literature are checked and verified. Our simulations clarify that a different mapping ratio between the coarse-grained models and the atomistically realistic description of polymers is required in a coarse-graining approach due to the different crossovers to the asymptotic behavior

  15. Comparison of shear bond strength of the stainless steel metallic brackets bonded by three bonding systems

    Directory of Open Access Journals (Sweden)

    Mehdi Ravadgar

    2013-09-01

    Full Text Available Introduction: In orthodontic treatment, it is essential to establish a satisfactory bond between enamel and bracket. After the self-etch primers (SEPs were introduced for the facilitation of bracket bonding in comparison to the conventional etch-and-bond system, multiple studies have been carried out on their shear bond strengths which have yielded different results. This study was aimed at comparing shear bond strengths of the stainless steel metallic brackets bonded by three bonding systems. Methods: In this experimental in vitro study, 60 extracted human maxillary premolar teeth were randomly divided into three equal groups: in the first group, Transbond XT (TBXT light cured composite was bonded with Transbond plus self-etching primer (TPSEP in the second group, TBXT composite was bonded with the conventional method of acid etching and in the third group, the self cured composite Unite TM bonding adhesive was bonded with the conventional method of acid etching. In all the groups, Standard edgewise-022 metallic brackets (American Orthodontics, Sheboygan, USA were used. Twenty-four hours after the completion of thermocycling, shear bond strength of brackets was measured by Universal Testing Machine (Zwick. In order to compare the shear bond strengths of the groups, the variance analysis test (ANOVA was adopted and p≤0.05 was considered as a significant level. Results: Based on megapascal, the average shear bond strength for the first, second, and third groups was 8.27±1.9, 9.78±2, and 8.92±2.5, respectively. There was no significant difference in the shear bond strength of the groups. Conclusions: Since TPSEP shear bond strength is approximately at the level of the conventional method of acid etching and within the desirable range for orthodontic brackets shear bond strength, applying TPSEP can serve as a substitute for the conventional method of etch and bond, particularly in orthodontic operations.

  16. Comparison of shear bond strength of the stainless steel metallic brackets bonded by three bonding systems

    Directory of Open Access Journals (Sweden)

    Mehdi Ravadgar

    2013-09-01

    Full Text Available Introduction: In orthodontic treatment, it is essential to establish a satisfactory bond between enamel and bracket. After the self-etch primers (SEPs were introduced for the facilitation of bracket bonding in comparison to the conventional etch-and-bond system, multiple studies have been carried out on their shear bond strengths which have yielded different results. This study was aimed at comparing shear bond strengths of the stainless steel metallic brackets bonded by three bonding systems. Methods: In this experimental in vitro study, 60 extracted human maxillary premolar teeth were randomly divided into three equal groups: in the first group, Transbond XT (TBXT light cured composite was bonded with Transbond plus self-etching primer (TPSEP; in the second group, TBXT composite was bonded with the conventional method of acid etching; and in the third group, the self cured composite Unite TM bonding adhesive was bonded with the conventional method of acid etching. In all the groups, Standard edgewise-022 metallic brackets (American Orthodontics, Sheboygan, USA were used. Twenty-four hours after the completion of thermocycling, shear bond strength of brackets was measured by Universal Testing Machine (Zwick. In order to compare the shear bond strengths of the groups, the variance analysis test (ANOVA was adopted and p≤0.05 was considered as a significant level. Results: Based on megapascal, the average shear bond strength for the first, second, and third groups was 8.27±1.9, 9.78±2, and 8.92±2.5, respectively. There was no significant difference in the shear bond strength of the groups. Conclusions: Since TPSEP shear bond strength is approximately at the level of the conventional method of acid etching and within the desirable range for orthodontic brackets shear bond strength, applying TPSEP can serve as a substitute for the conventional method of etch and bond, particularly in orthodontic operations.

  17. Tribological Behavior of TiC/a-C : H-Coated and Uncoated Steels Sliding Against Phenol-Formaldehyde Composite Reinforced with PTFE and Glass Fibers

    NARCIS (Netherlands)

    Shen, J.T.; Pei, Y.T.; Hosson, J.Th.M. De

    2013-01-01

    Tribological experiments on phenol-formaldehyde composite reinforced with polytetrafluoroethylene (PTFE) and glass fibers were performed against 100Cr6 steel and TiC/a-C:H thin film-coated 100Cr6 steel. In both cases, the coefficient of friction increases with increasing sliding distance until a

  18. Tuning of the microstructure, mechanical and tribological properties of a-C:H films by bias voltage of high frequency unipolar pulse

    International Nuclear Information System (INIS)

    Wang, Jia; Cao, Zhongyue; Pan, Fuping; Wang, Fuguo; Liang, Aimin; Zhang, Junyan

    2015-01-01

    Highlights: • a-C:H films deposited by high frequency unipolar pulse PECVD. • The film structures can be adjusted by bias voltage. • More graphitic structures form at high bias voltage. • The mechanical and tribological properties are improved by these structures. - Abstract: Amorphous hydrogenated carbon (a-C:H) films were prepared by high frequency unipolar pulse plasma-enhanced chemical vapor deposition in CH 4 , Ar, and H 2 atmosphere with the bias voltage in the range of −800 –−1600 V. The microstructures and mechanical properties of a-C:H films were investigated via high resolution transmission electron microscope (HRTEM), Raman spectroscopy, and Nanoindenter. The results reveal that the curved and straight graphitic microstructures appear in amorphous carbon matrix, and their contents increase obviously with the bias voltage. At the same time, the corresponding hardness decreases and elastic recovery increases, however even in such a case films still possess excellent mechanical properties. According to the tribological property characterization, we believe that the bias voltage also influences their tribological performances significantly, the higher the bias voltage finally gets, the lower the friction coefficient and wear rate occur. These results indicate that the microstructures of a-C:H films can be tuned efficiently by bias voltage and the films with good mechanical and tribological properties can be obtained at a higher range.

  19. Tuning of the microstructure, mechanical and tribological properties of a-C:H films by bias voltage of high frequency unipolar pulse

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jia; Cao, Zhongyue; Pan, Fuping [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Wang, Fuguo, E-mail: fgwang@licp.cas.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Liang, Aimin [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Zhang, Junyan, E-mail: zhangjunyan@licp.cas.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2015-11-30

    Highlights: • a-C:H films deposited by high frequency unipolar pulse PECVD. • The film structures can be adjusted by bias voltage. • More graphitic structures form at high bias voltage. • The mechanical and tribological properties are improved by these structures. - Abstract: Amorphous hydrogenated carbon (a-C:H) films were prepared by high frequency unipolar pulse plasma-enhanced chemical vapor deposition in CH{sub 4}, Ar, and H{sub 2} atmosphere with the bias voltage in the range of −800 –−1600 V. The microstructures and mechanical properties of a-C:H films were investigated via high resolution transmission electron microscope (HRTEM), Raman spectroscopy, and Nanoindenter. The results reveal that the curved and straight graphitic microstructures appear in amorphous carbon matrix, and their contents increase obviously with the bias voltage. At the same time, the corresponding hardness decreases and elastic recovery increases, however even in such a case films still possess excellent mechanical properties. According to the tribological property characterization, we believe that the bias voltage also influences their tribological performances significantly, the higher the bias voltage finally gets, the lower the friction coefficient and wear rate occur. These results indicate that the microstructures of a-C:H films can be tuned efficiently by bias voltage and the films with good mechanical and tribological properties can be obtained at a higher range.

  20. One-pot synthesis of multisubstituted 2-aminoquinolines from annulation of 1-aryl tetrazoles with internal alkynes via double C-H activation and denitrogenation.

    Science.gov (United States)

    Zhang, Lei; Zheng, Liyao; Guo, Biao; Hua, Ruimao

    2014-12-05

    An efficient, one-pot synthesis of multisubstituted 2-aminoquinolines from 1-aryl tetrazoles and internal alkynes has been developed. The reaction involves cyclization of 1-aryl tetrazoles with internal alkynes via rhodium(III)-catalyzed double C-H activation and copper(II)-mediated denitrogenation.

  1. Improving the back surface field on an amorphous silicon carbide (a-SiC:H) thin film photocathode for solar water splitting

    NARCIS (Netherlands)

    Perez Rodriguez, P.; Cardenas-Morcoso, Drialys; Digdaya, I.A.; Mangel Raventos, A.; Procel Moya, P.A.; Isabella, O.; Gimenez, Sixto; Zeman, M.; Smith, W.A.; Smets, A.H.M.

    2018-01-01

    Amorphous silicon carbide (a-SiC:H) is a promising material for photoelectrochemical water splitting owing to its relatively small band-gap energy and high chemical and optoelectrical stability. This work studies the interplay between charge-carrier separation and collection, and their injection

  2. Hydrogen insertion in titanium carbide based thin films (nc-TiC{sub x}/a-C:H) - comparison with bulk TiC{sub x}

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Julien; Jaoul, Cédric, E-mail: jaoul@ensil.unilim.fr; Glandut, Nicolas; Lefort, Pierre

    2016-08-01

    Nanocomposites composed of titanium carbide nanosized grains embedded in an amorphous hydrogenated carbon matrix (nc-TiC{sub x}/a-C:H) are prepared by hybrid Magnetron Sputtering - PECVD process using a titanium metal target and gaseous C{sub 6}H{sub 6}. By controlling the benzene flow rate, thin films with different carbon content are obtained. The structures of nc-TiC{sub x}/a-C:H materials are analyzed by X-ray diffraction, X-ray photoelectron and Raman spectroscopic methods. The electrochemical hydrogen insertion, as studied by cyclic voltammetry, strongly depends on the carbon content in the thin films. The correlation between the hydrogen insertion ability and the structure of materials are discussed. Furthermore, we show that the hydrogen insertion in these thin films reaches values much more significant than in bulk substoichiometric titanium carbide obtained by reactive sintering. - Highlights: • nc-TiC{sub x}/a-C:H thin films are prepared hybrid Magnetron Sputtering - PECVD process. • Different carbon contents are obtained by changing the hydrocarbon flowrate. • Expanded lattice parameter of the TiC{sub x} phase and a-C:H phase are observed. • Electrochemical hydrogen insertion strongly depends on the carbon content. • The maximum insertion is 22 times more important than bulk TiC{sub x}.

  3. Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis

    Science.gov (United States)

    Houben, Els; De Preter, Vicky; Billen, Jaak; Van Ranst, Marc; Verbeke, Kristin

    2015-01-01

    The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2) excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO), and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO. PMID:26371034

  4. Process control by optical emission spectroscopy during growth of a-C:H from a CH4 plasma by plasma-enhanced chemical vapour deposition

    DEFF Research Database (Denmark)

    Barholm-Hansen, C; Bentzon, MD; Vigild, Martin Etchells

    1994-01-01

    During the growth of a-C:H thin films for tribological applications, the characteristic optical emission from a CH4 plasma was used to estimate growth conditions such as the degree of dissociation of the feed gas, the deposition rate and the presence of impurities. Films were fabricated with vari...

  5. Why are Hydrogen Bonds Directional?

    Indian Academy of Sciences (India)

    century and most chemists appear to think of 'chemi- cal bond' as ..... These complexes, in their global min- ima, have ... taneously act as hydrogen bond donor and acceptor displaying ... also has a local minimum, which is linear and similar to.

  6. Bond yield curve construction

    Directory of Open Access Journals (Sweden)

    Kožul Nataša

    2014-01-01

    Full Text Available In the broadest sense, yield curve indicates the market's view of the evolution of interest rates over time. However, given that cost of borrowing it closely linked to creditworthiness (ability to repay, different yield curves will apply to different currencies, market sectors, or even individual issuers. As government borrowing is indicative of interest rate levels available to other market players in a particular country, and considering that bond issuance still remains the dominant form of sovereign debt, this paper describes yield curve construction using bonds. The relationship between zero-coupon yield, par yield and yield to maturity is given and their usage in determining curve discount factors is described. Their usage in deriving forward rates and pricing related derivative instruments is also discussed.

  7. A Monte Carlo algorithm for sampling rare events: application to a search for the Griffiths singularity

    International Nuclear Information System (INIS)

    Hukushima, K; Iba, Y

    2008-01-01

    We develop a recently proposed importance-sampling Monte Carlo algorithm for sampling rare events and quenched variables in random disordered systems. We apply it to a two dimensional bond-diluted Ising model and study the Griffiths singularity which is considered to be due to the existence of rare large clusters. It is found that the distribution of the inverse susceptibility has an exponential tail down to the origin which is considered the consequence of the Griffiths singularity

  8. Corporate Hybrid Bonds

    OpenAIRE

    Ahlberg, Johan; Jansson, Anton

    2016-01-01

    Hybrid securities do not constitute a new phenomenon in the Swedish capital markets. Most commonly, hybrids issued by Swedish real estate companies in recent years are preference shares. Corporate hybrid bonds on the other hand may be considered as somewhat of a new-born child in the family of hybrid instruments. These do, as all other hybrid securities, share some equity-like and some debt-like characteristics. Nevertheless, since 2013 the interest for the instrument has grown rapidly and ha...

  9. Hybrid Cat Bonds

    OpenAIRE

    Barrieu, Pauline; Louberge, Henri

    2009-01-01

    Natural catastrophes attract regularly the attention of media and have become a source of public concern. From a financial viewpoint, natural catastrophes represent idiosyncratic risks, diversifiable at the world level. But for reasons analyzed in this paper reinsurance markets are unable to cope with this risk completely. Insurance-linked securities, such as cat bonds, have been issued to complete the international risk transfer process, but their development is disappointing so far. This pa...

  10. Cuartel San Carlos. Yacimiento veterano

    Directory of Open Access Journals (Sweden)

    Mariana Flores

    2007-01-01

    Full Text Available El Cuartel San Carlos es un monumento histórico nacional (1986 de finales del siglo XVIII (1785-1790, caracterizado por sufrir diversas adversidades en su construcción y soportar los terremotos de 1812 y 1900. En el año 2006, el organismo encargado de su custodia, el Instituto de Patrimonio Cultural del Ministerio de Cultura, ejecutó tres etapas de exploración arqueológica, que abarcaron las áreas Traspatio, Patio Central y las Naves Este y Oeste de la edificación. Este trabajo reseña el análisis de la documentación arqueológica obtenida en el sitio, a partir de la realización de dicho proyecto, denominado EACUSAC (Estudio Arqueológico del Cuartel San Carlos, que representa además, la tercera campaña realizada en el sitio. La importancia de este yacimiento histórico, radica en su participación en los acontecimientos que propiciaron conflictos de poder durante el surgimiento de la República y en los sucesos políticos del siglo XX. De igual manera, se encontró en el sitio una amplia muestra de materiales arqueológicos que reseñan un estilo de vida cotidiana militar, así como las dinámicas sociales internas ocurridas en el San Carlos, como lugar estratégico para la defensa de los diferentes regímenes que atravesó el país, desde la época del imperialismo español hasta nuestros días.

  11. Carlos Battilana: Profesor, Gestor, Amigo

    Directory of Open Access Journals (Sweden)

    José Pacheco

    2009-12-01

    Full Text Available El Comité Editorial de Anales ha perdido a uno de sus miembros más connotados. Brillante docente de nuestra Facultad, Carlos Alberto Battilana Guanilo (1945-2009 supo transmitir los conocimientos y atraer la atención de sus auditorios, de jóvenes estudiantes o de contemporáneos ya no tan jóvenes. Interesó a sus alumnos en la senda de la capacitación permanente y en la investigación. Por otro lado, comprometió a médicos distinguidos a conformar y liderar grupos con interés en la ciencia-amistad. Su vocación docente lo vinculó a facultades de medicina y academias y sociedades científicas, en donde coordinó cursos y congresos de grato recuerdo. Su producción científica la dedicó a la nefrología, inmunología, cáncer, costos en el tratamiento médico. Su capacidad gestora y de liderazgo presente desde su época de estudiante, le permitió llegar a ser director regional de un laboratorio farmacéutico de mucho prestigio, organizar una facultad de medicina y luego tener el cargo de decano de la facultad de ciencias de la salud de dicha universidad privada. Carlos fue elemento importante para que Anales alcanzara un sitial de privilegio entre las revistas biomédicas peruanas. En la semblanza que publicamos tratamos de resumir apretadamente la trayectoria de Carlos Battilana, semanas después de su partida sin retorno.

  12. Monte Carlo Particle Lists: MCPL

    DEFF Research Database (Denmark)

    Kittelmann, Thomas; Klinkby, Esben Bryndt; Bergbäck Knudsen, Erik

    2017-01-01

    A binary format with lists of particle state information, for interchanging particles between various Monte Carlo simulation applications, is presented. Portable C code for file manipulation is made available to the scientific community, along with converters and plugins for several popular...... simulation packages. Program summary: Program Title: MCPL. Program Files doi: http://dx.doi.org/10.17632/cby92vsv5g.1 Licensing provisions: CC0 for core MCPL, see LICENSE file for details. Programming language: C and C++ External routines/libraries: Geant4, MCNP, McStas, McXtrace Nature of problem: Saving...

  13. Luis Carlos López

    Directory of Open Access Journals (Sweden)

    Rafael Maya

    1979-04-01

    Full Text Available Entre los poetasa del Centenario tuvo Luis Carlos López mucha popularidad en el extranjero, desde la publicación de su primer libro. Creo que su obra llamó la atención de filósofos como Unamuno y, si no estoy equivocado, Darío se refirió a ella en términos elogiosos. En Colombia ha sido encomiada hiperbólicamente por algunos, a tiemp que otros no le conceden mayor mérito.

  14. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    The paper examines the role of structured bonds in the optimal portfolio of a small retail investor. We consider the typical structured bond essentially repacking an exotic option and a zero coupon bond, i.e. an investment with portfolio insurance. The optimal portfolio is found when the investment...

  15. 46 CFR Sec. 10 - Bonds.

    Science.gov (United States)

    2010-10-01

    ... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form 25...

  16. The chemical bond in inorganic chemistry the bond valence model

    CERN Document Server

    Brown, I David

    2016-01-01

    The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

  17. Monte Carlo techniques in radiation therapy

    CERN Document Server

    Verhaegen, Frank

    2013-01-01

    Modern cancer treatment relies on Monte Carlo simulations to help radiotherapists and clinical physicists better understand and compute radiation dose from imaging devices as well as exploit four-dimensional imaging data. With Monte Carlo-based treatment planning tools now available from commercial vendors, a complete transition to Monte Carlo-based dose calculation methods in radiotherapy could likely take place in the next decade. Monte Carlo Techniques in Radiation Therapy explores the use of Monte Carlo methods for modeling various features of internal and external radiation sources, including light ion beams. The book-the first of its kind-addresses applications of the Monte Carlo particle transport simulation technique in radiation therapy, mainly focusing on external beam radiotherapy and brachytherapy. It presents the mathematical and technical aspects of the methods in particle transport simulations. The book also discusses the modeling of medical linacs and other irradiation devices; issues specific...

  18. Mean field simulation for Monte Carlo integration

    CERN Document Server

    Del Moral, Pierre

    2013-01-01

    In the last three decades, there has been a dramatic increase in the use of interacting particle methods as a powerful tool in real-world applications of Monte Carlo simulation in computational physics, population biology, computer sciences, and statistical machine learning. Ideally suited to parallel and distributed computation, these advanced particle algorithms include nonlinear interacting jump diffusions; quantum, diffusion, and resampled Monte Carlo methods; Feynman-Kac particle models; genetic and evolutionary algorithms; sequential Monte Carlo methods; adaptive and interacting Marko

  19. Monte Carlo surface flux tallies

    International Nuclear Information System (INIS)

    Favorite, Jeffrey A.

    2010-01-01

    Particle fluxes on surfaces are difficult to calculate with Monte Carlo codes because the score requires a division by the surface-crossing angle cosine, and grazing angles lead to inaccuracies. We revisit the standard practice of dividing by half of a cosine 'cutoff' for particles whose surface-crossing cosines are below the cutoff. The theory behind this approximation is sound, but the application of the theory to all possible situations does not account for two implicit assumptions: (1) the grazing band must be symmetric about 0, and (2) a single linear expansion for the angular flux must be applied in the entire grazing band. These assumptions are violated in common circumstances; for example, for separate in-going and out-going flux tallies on internal surfaces, and for out-going flux tallies on external surfaces. In some situations, dividing by two-thirds of the cosine cutoff is more appropriate. If users were able to control both the cosine cutoff and the substitute value, they could use these parameters to make accurate surface flux tallies. The procedure is demonstrated in a test problem in which Monte Carlo surface fluxes in cosine bins are converted to angular fluxes and compared with the results of a discrete ordinates calculation.

  20. Hydrogen bonding in ionic liquids.

    Science.gov (United States)

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-07

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

  1. Tracing the Fingerprint of Chemical Bonds within the Electron Densities of Hydrocarbons: A Comparative Analysis of the Optimized and the Promolecule Densities.

    Science.gov (United States)

    Keyvani, Zahra Alimohammadi; Shahbazian, Shant; Zahedi, Mansour

    2016-10-18

    The equivalence of the molecular graphs emerging from the comparative analysis of the optimized and the promolecule electron densities in two hundred and twenty five unsubstituted hydrocarbons was recently demonstrated [Keyvani et al. Chem. Eur. J. 2016, 22, 5003]. Thus, the molecular graph of an optimized molecular electron density is not shaped by the formation of the C-H and C-C bonds. In the present study, to trace the fingerprint of the C-H and C-C bonds in the electron densities of the same set of hydrocarbons, the amount of electron density and its Laplacian at the (3, -1) critical points associated with these bonds are derived from both optimized and promolecule densities, and compared in a newly proposed comparative analysis. The analysis not only conforms to the qualitative picture of the electron density build up between two atoms upon formation of a bond in between, but also quantifies the resulting accumulation of the electron density at the (3, -1) critical points. The comparative analysis also reveals a unified mode of density accumulation in the case of 2318 studied C-H bonds, but various modes of density accumulation are observed in the case of 1509 studied C-C bonds and they are classified into four groups. The four emerging groups do not always conform to the traditional classification based on the bond orders. Furthermore, four C-C bonds described as exotic bonds in previous studies, for example the inverted C-C bond in 1,1,1-propellane, are naturally distinguished from the analysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Monte Carlo simulations of neutron scattering instruments

    International Nuclear Information System (INIS)

    Aestrand, Per-Olof; Copenhagen Univ.; Lefmann, K.; Nielsen, K.

    2001-01-01

    A Monte Carlo simulation is an important computational tool used in many areas of science and engineering. The use of Monte Carlo techniques for simulating neutron scattering instruments is discussed. The basic ideas, techniques and approximations are presented. Since the construction of a neutron scattering instrument is very expensive, Monte Carlo software used for design of instruments have to be validated and tested extensively. The McStas software was designed with these aspects in mind and some of the basic principles of the McStas software will be discussed. Finally, some future prospects are discussed for using Monte Carlo simulations in optimizing neutron scattering experiments. (R.P.)

  3. On the use of stochastic approximation Monte Carlo for Monte Carlo integration

    KAUST Repository

    Liang, Faming

    2009-01-01

    The stochastic approximation Monte Carlo (SAMC) algorithm has recently been proposed as a dynamic optimization algorithm in the literature. In this paper, we show in theory that the samples generated by SAMC can be used for Monte Carlo integration

  4. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper

    2015-01-01

    The structure of insulin, a glucose homeostasis-controlling hormone, is highly conserved in all vertebrates and stabilized by three disulfide bonds. Recently, we designed a novel insulin analogue containing a fourth disulfide bond located between positions A10-B4. The N-terminus of insulin's B......-chain is flexible and can adapt multiple conformations. We examined how well disulfide bond predictions algorithms could identify disulfide bonds in this region of insulin. In order to identify stable insulin analogues with additional disulfide bonds, which could be expressed, the Cβ cut-off distance had...... in comparison to analogues with additional disulfide bonds that were more difficult to predict. In contrast, addition of the fourth disulfide bond rendered all analogues resistant to fibrillation under stress conditions and all stable analogues bound to the insulin receptor with picomolar affinities. Thus...

  5. Sequence Variations in the Flagellar Antigen Genes fliC H25 and fliC H28 of Escherichia coli and Their Use in Identification and Characterization of Enterohemorrhagic E. coli (EHEC) O145:H25 and O145:H28

    Science.gov (United States)

    Beutin, Lothar; Delannoy, Sabine; Fach, Patrick

    2015-01-01

    Enterohemorrhagic E. coli (EHEC) serogroup O145 is regarded as one of the major EHEC serogroups involved in severe infections in humans. EHEC O145 encompasses motile and non-motile strains of serotypes O145:H25 and O145:H28. Sequencing the fliC-genes associated with the flagellar antigens H25 and H28 revealed the genetic diversity of the fliC H25 and fliC H28 gene sequences in E. coli. Based on allele discrimination of these fliC-genes real-time PCR tests were designed for identification of EHEC O145:H25 and O145:H28. The fliC H25 genes present in O145:H25 were found to be very similar to those present in E. coli serogroups O2, O100, O165, O172 and O177 pointing to their common evolution but were different from fliC H25 genes of a multiple number of other E. coli serotypes. In a similar way, EHEC O145:H28 harbor a characteristic fliC H28 allele which, apart from EHEC O145:H28, was only found in enteropathogenic (EPEC) O28:H28 strains that shared some common traits with EHEC O145:H28. The real time PCR-assays targeting these fliC H25[O145] and fliC H28[O145] alleles allow better characterization of EHEC O145:H25 and EHEC O145:H28. Evaluation of these PCR assays in spiked ready-to eat salad samples resulted in specific detection of both types of EHEC O145 strains even when low spiking levels of 1–10 cfu/g were used. Furthermore these PCR assays allowed identification of non-motile E. coli strains which are serologically not typable for their H-antigens. The combined use of O-antigen genotyping (O145wzy) and detection of the respective fliC H25[O145] and fliC H28[O145] allele types contributes to improve identification and molecular serotyping of E. coli O145 isolates. PMID:26000885

  6. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    International Nuclear Information System (INIS)

    Lichtenberger, D.L.

    1991-10-01

    The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of (η 5 -C 5 H 4 X)Rh(CO) 2 complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C 60 molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C 60 reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs

  7. Direct C-H Arylation Meets Perovskite Solar Cells: Sn-Free Synthesis Shortcut to High Performance Hole-Transporting Materials.

    Science.gov (United States)

    Chang, Yu-Chieh; Lee, Kun-Mu; Lai, Chia-Hsin; Liu, Ching-Yuan

    2018-03-30

    In contrast to the traditional multistep synthesis, we demonstrate herein a two-step synthesis-shortcut to triphenylamine-based hole-transporting materials (HTMs) through sequential direct C-H arylations. These hole-transporting molecules are fabricated in perovskite-based solar cells (PSCs), exhibiting promising efficiencies up to 17.69%, which is comparable to PSCs utilizing the commercially available spiro-OMeTAD as HTM. This is the first report describing the use of step-saving C-H activations/arylations in the facile synthesis of small-molecule HTMs for perovskite solar cells. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Limits on top FCNC decay t$\\rightarrow$cH and t$\\rightarrow$c$\\gamma$ from CLIC at 380 GeV

    CERN Document Server

    Zarnecki, Aleksander

    2018-01-01

    FCNC top decays are very strongly suppressed in the Standard Model and the observation of any such decay would be a direct signature of physics beyond SM. Many "new physics" scenarios predict contributions to FCNC processes and the largest enhancement in many models is for t$\\rightarrow$cH decay. Enhancements for the decay channel t$\\rightarrow$c$\\gamma$ are more modest, but the decay still has a clearly identifiable kinematic signature. Prospects for measuring these decays at CLIC running at 380 GeV were studied with full detector simulation, taking the luminosity distribution, beam polarization and beam induced background into account. Top pair production events with t$\\rightarrow$cH decays can be identified based on the kinematic constraints and flavour tagging information. The analysis was divided into three steps: classification of top pair candidate events, event quality determination and kinematic reconstruction based on signal or background hypotheses, and final separation of signal from background. T...

  9. A General Cp*CoIII -Catalyzed Intramolecular C-H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine, and Tylophora Alkaloids.

    Science.gov (United States)

    Lerchen, Andreas; Knecht, Tobias; Koy, Maximilian; Daniliuc, Constantin G; Glorius, Frank

    2017-09-07

    Herein, we report a Cp*Co III -catalyzed C-H activation approach as the key step to create highly valuable isoquinolones and pyridones as building blocks that can readily be applied in the total syntheses of a variety of aromathecin, protoberberine, and tylophora alkaloids. This particular C-H activation/annulation reaction was achieved with several terminal as well as internal alkyne coupling partners delivering a broad scope with excellent functional group tolerance. The synthetic applicability of this protocol reported herein was demonstrated in the total syntheses of two Topo-I-Inhibitors and two 8-oxyprotoberberine cores that can be further elaborated into the tetrahydroprotoberberine and the protoberberine alkaloid core. Moreover these building blocks were also transformed to six different tylophora alkaloids in expedient fashion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

    Science.gov (United States)

    Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata

    2017-01-18

    Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

  11. General Monte Carlo code MONK

    International Nuclear Information System (INIS)

    Moore, J.G.

    1974-01-01

    The Monte Carlo code MONK is a general program written to provide a high degree of flexibility to the user. MONK is distinguished by its detailed representation of nuclear data in point form i.e., the cross-section is tabulated at specific energies instead of the more usual group representation. The nuclear data are unadjusted in the point form but recently the code has been modified to accept adjusted group data as used in fast and thermal reactor applications. The various geometrical handling capabilities and importance sampling techniques are described. In addition to the nuclear data aspects, the following features are also described; geometrical handling routines, tracking cycles, neutron source and output facilities. 12 references. (U.S.)

  12. Monte Carlo lattice program KIM

    International Nuclear Information System (INIS)

    Cupini, E.; De Matteis, A.; Simonini, R.

    1980-01-01

    The Monte Carlo program KIM solves the steady-state linear neutron transport equation for a fixed-source problem or, by successive fixed-source runs, for the eigenvalue problem, in a two-dimensional thermal reactor lattice. Fluxes and reaction rates are the main quantities computed by the program, from which power distribution and few-group averaged cross sections are derived. The simulation ranges from 10 MeV to zero and includes anisotropic and inelastic scattering in the fast energy region, the epithermal Doppler broadening of the resonances of some nuclides, and the thermalization phenomenon by taking into account the thermal velocity distribution of some molecules. Besides the well known combinatorial geometry, the program allows complex configurations to be represented by a discrete set of points, an approach greatly improving calculation speed

  13. Monte Carlo simulation of experiments

    International Nuclear Information System (INIS)

    Opat, G.I.

    1977-07-01

    An outline of the technique of computer simulation of particle physics experiments by the Monte Carlo method is presented. Useful special purpose subprograms are listed and described. At each stage the discussion is made concrete by direct reference to the programs SIMUL8 and its variant MONTE-PION, written to assist in the analysis of the radiative decay experiments μ + → e + ν sub(e) antiνγ and π + → e + ν sub(e)γ, respectively. These experiments were based on the use of two large sodium iodide crystals, TINA and MINA, as e and γ detectors. Instructions for the use of SIMUL8 and MONTE-PION are given. (author)

  14. Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo[ de]chromenes.

    Science.gov (United States)

    Fang, Feifei; Zhang, Chunmei; Zhou, Chaofan; Li, Yazhou; Zhou, Yu; Liu, Hong

    2018-04-06

    Rh (III)-catalyzed C-H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[ de]chromenes via a formal (4 + 2) cycloaddition with a diazo compound and subsequent tandem (4 + 2) cycloaddition with another diazo compound. Intriguingly, synthesis of substituted benzo[ de]chromenes and their decarboxylation products could be realized by controlling the reaction conditions. These reactions have a broad range of substrates, moderate to good yields, and high regioselectivity.

  15. Synthesis of Donor/Acceptor-Substituted Diazo Compounds in Flow and Their Application in Enantioselective Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.

    Science.gov (United States)

    Rackl, Daniel; Yoo, Chun-Jae; Jones, Christopher W; Davies, Huw M L

    2017-06-16

    A tandem reaction system has been developed for the preparation of donor/acceptor-substituted diazo compounds in continuous flow coupled to dirhodium-catalyzed C-H functionalization or cyclopropanation. Hydrazones were oxidized in flow by solid-supported N-iodo-p-toluenesulfonamide potassium salt (PS-SO 2 NIK) to generate the diazo compounds, which were then purified by passing through a column of molecular sieves/sodium thiosulfate.

  16. Linear antenna microwave plasma CVD diamond deposition at the edge of no-growth region of C-H-O ternary diagram

    Czech Academy of Sciences Publication Activity Database

    Potocký, Štěpán; Babchenko, Oleg; Hruška, Karel; Kromka, Alexander

    2012-01-01

    Roč. 249, č. 12 (2012), s. 2612-2615 ISSN 0370-1972 R&D Projects: GA ČR(CZ) GBP108/12/G108; GA ČR GAP205/12/0908 Institutional research plan: CEZ:AV0Z10100521 Keywords : C-H-O phase diagram * nanocrystalline diamond * plasma enhanced CVD * Raman spectroscopy * SEM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.489, year: 2012

  17. Tandem Rh-Catalyzed Oxidative C-H Olefination and Cyclization of Enantiomerically Enriched Benzo-1,3-Sulfamidates: Stereoselective Synthesis of trans-1,3-Disubstituted Isoindolines.

    Science.gov (United States)

    Achary, Raghavendra; Jung, In-A; Lee, Hyeon-Kyu

    2018-04-06

    A tandem process, involving Rh(III)-catalyzed oxidative C-H olefination of enantiomerically enriched 4-aryl-benzo-1,3-sulfamidates and subsequent intramolecular aza-Michael cyclization has been developed. The reaction produces trans-benzosulfamidate-fused-1,3-disubstituted isoindolines as major products, in which the configurational integrity of the stereogenic center in the starting material is preserved. Further transformations of the benzosulfamidate-fused-1,3-disubstituted isoindolines are described.

  18. Die teologiese skool in die P.U.K vir C.H.O.: met die betekenis van die teologiese skool vir die Christelike wetenskap

    Directory of Open Access Journals (Sweden)

    F. Postma

    1944-03-01

    Full Text Available Die Teologiese Skool van die Gereformeerde Kerk gedink op 29 November 1944 sy vyf-en-sewentigjarige bestaan.Die Raad en Senaat van die P.U.K. vir C.H.O. wil ook langs hierdie weg die Teologiese Skool van harte gelukwens en die versekering gee dat daar by die outoriteite van die P.U.K. ’n diepgevoelde dankbaarheid heers dat hierdie inrigting sovele jare deur onse God en Vader gedra en gespaar is.

  19. Advanced Computational Methods for Monte Carlo Calculations

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Forrest B. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2018-01-12

    This course is intended for graduate students who already have a basic understanding of Monte Carlo methods. It focuses on advanced topics that may be needed for thesis research, for developing new state-of-the-art methods, or for working with modern production Monte Carlo codes.

  20. Nested Sampling with Constrained Hamiltonian Monte Carlo

    OpenAIRE

    Betancourt, M. J.

    2010-01-01

    Nested sampling is a powerful approach to Bayesian inference ultimately limited by the computationally demanding task of sampling from a heavily constrained probability distribution. An effective algorithm in its own right, Hamiltonian Monte Carlo is readily adapted to efficiently sample from any smooth, constrained distribution. Utilizing this constrained Hamiltonian Monte Carlo, I introduce a general implementation of the nested sampling algorithm.

  1. Structure and weak hydrogen bonds in liquid acetaldehyde

    Directory of Open Access Journals (Sweden)

    Cordeiro Maria A. M.

    2004-01-01

    Full Text Available Monte Carlo simulations have been performed to investigate the structure and hydrogen bonds formation in liquid acetaldehyde. An all atom model for the acetaldehyde have been optimized in the present work. Theoretical values obtained for heat of vaporisation and density of the liquid are in good agreement with experimental data. Graphics of radial distribution function indicate a well structured liquid compared to other similar dipolar organic liquids. Molecular mechanics minimization in gas phase leads to a trimer of very stable structure. The geometry of this complex is in very good agreement with the rdf. The shortest site-site correlation is between oxygen and the carbonyl hydrogen, suggesting that this correlation play a important role in the liquid structure and properties. The OxxxH average distance and the C-HxxxO angle obtained are characteristic of weak hydrogen bonds.

  2. Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes.

    Science.gov (United States)

    Sun, Bo; Yoshino, Tatsuhiko; Kanai, Motomu; Matsunaga, Shigeki

    2015-10-26

    The synthesis of isoquinolines by site-selective C-H activation of O-acyl oximes with a Cp*Co(III) catalyst is described. In the presence of this catalyst, the C-H activation of various unsymmetrically substituted O-acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98 % yield. Whereas the reactions catalyzed by the Cp*Co(III) system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh(III) catalysts led to low selectivities and/or yields when unsymmetrical O-acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the C-H activation step under Cp*Co(III) and Cp*Rh(III) catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Monte Carlo Treatment Planning for Advanced Radiotherapy

    DEFF Research Database (Denmark)

    Cronholm, Rickard

    This Ph.d. project describes the development of a workflow for Monte Carlo Treatment Planning for clinical radiotherapy plans. The workflow may be utilized to perform an independent dose verification of treatment plans. Modern radiotherapy treatment delivery is often conducted by dynamically...... modulating the intensity of the field during the irradiation. The workflow described has the potential to fully model the dynamic delivery, including gantry rotation during irradiation, of modern radiotherapy. Three corner stones of Monte Carlo Treatment Planning are identified: Building, commissioning...... and validation of a Monte Carlo model of a medical linear accelerator (i), converting a CT scan of a patient to a Monte Carlo compliant phantom (ii) and translating the treatment plan parameters (including beam energy, angles of incidence, collimator settings etc) to a Monte Carlo input file (iii). A protocol...

  4. The MC21 Monte Carlo Transport Code

    International Nuclear Information System (INIS)

    Sutton TM; Donovan TJ; Trumbull TH; Dobreff PS; Caro E; Griesheimer DP; Tyburski LJ; Carpenter DC; Joo H

    2007-01-01

    MC21 is a new Monte Carlo neutron and photon transport code currently under joint development at the Knolls Atomic Power Laboratory and the Bettis Atomic Power Laboratory. MC21 is the Monte Carlo transport kernel of the broader Common Monte Carlo Design Tool (CMCDT), which is also currently under development. The vision for CMCDT is to provide an automated, computer-aided modeling and post-processing environment integrated with a Monte Carlo solver that is optimized for reactor analysis. CMCDT represents a strategy to push the Monte Carlo method beyond its traditional role as a benchmarking tool or ''tool of last resort'' and into a dominant design role. This paper describes various aspects of the code, including the neutron physics and nuclear data treatments, the geometry representation, and the tally and depletion capabilities

  5. Monte Carlo simulation in nuclear medicine

    International Nuclear Information System (INIS)

    Morel, Ch.

    2007-01-01

    The Monte Carlo method allows for simulating random processes by using series of pseudo-random numbers. It became an important tool in nuclear medicine to assist in the design of new medical imaging devices, optimise their use and analyse their data. Presently, the sophistication of the simulation tools allows the introduction of Monte Carlo predictions in data correction and image reconstruction processes. The availability to simulate time dependent processes opens up new horizons for Monte Carlo simulation in nuclear medicine. In a near future, these developments will allow to tackle simultaneously imaging and dosimetry issues and soon, case system Monte Carlo simulations may become part of the nuclear medicine diagnostic process. This paper describes some Monte Carlo method basics and the sampling methods that were developed for it. It gives a referenced list of different simulation software used in nuclear medicine and enumerates some of their present and prospective applications. (author)

  6. Fatigue aging of adhesive bonds

    International Nuclear Information System (INIS)

    DeLollis, N.J.

    1979-01-01

    A year long study has been made of the effect of fatigue on the bond between two epoxy encapsulant formulations and a fused alumina disc. The variables studied included isothermal aging at temperatures up to and including the cure temperature and cyclic thermal aging from +74 to -54 0 C. The encapsulants were glass microballoon filled epoxies differing only in curing agents. One was cured with an aromatic amine eutectic (Shell Curing Agent Z). The other was cured with diethanolamine. The Z cured encapsulant bond failed completely at the bond interface with little or no aging; infrared evidence indicated a soluble interlayer as a possible cause of failure. The diethanolamine cured encapsulant survived a year of isothermal aging with little or no evidence of bond degradation. Cyclic thermal aging resulted in gradual bond failure with time. An extrapolation of the cyclic aging data indicates that the stresses induced by thermal cycling would result in complete bond failure in about 1200 days

  7. What is a hydrogen bond?

    Indian Academy of Sciences (India)

    First page Back Continue Last page Overview Graphics. What is a hydrogen bond? Precise definition of a hydrogen bond is still elusive!1. Several criteria are listed usually for X-H•••Y, X and Y initially thought to be F, O and N only1. Structural: The X-Y bond length is less than the sum of their van der Waals radii. X-H•••Y is ...

  8. Composite interlayer for diffusion bonding

    International Nuclear Information System (INIS)

    1976-01-01

    A ductile interlayer is described, which is useful for transient liquid phase diffusion bonding of metallic articles; the interlayer consisting of a melting point depressant and a plurality of ductile lamellae which are free from carbides, aluminides and borides. The composition and fabrication of the lamellae, and the process for bonding the metallic articles, depend on the composition of the metals to be bonded, and are exemplified in the specification. (U.K.)

  9. Wafer bonding applications and technology

    CERN Document Server

    Gösele, Ulrich

    2004-01-01

    During the past decade direct wafer bonding has developed into a mature materials integration technology. This book presents state-of-the-art reviews of the most important applications of wafer bonding written by experts from industry and academia. The topics include bonding-based fabrication methods of silicon-on-insulator, photonic crystals, VCSELs, SiGe-based FETs, MEMS together with hybrid integration and laser lift-off. The non-specialist will learn about the basics of wafer bonding and its various application areas, while the researcher in the field will find up-to-date information about this fast-moving area, including relevant patent information.

  10. A simplified indirect bonding technique

    Directory of Open Access Journals (Sweden)

    Radha Katiyar

    2014-01-01

    Full Text Available With the advent of lingual orthodontics, indirect bonding technique has become an integral part of practice. It involves placement of brackets initially on the models and then their transfer to teeth with the help of transfer trays. Problems encountered with current indirect bonding techniques used are (1 the possibility of adhesive flash remaining around the base of the brackets which requires removal (2 longer time required for the adhesive to gain enough bond strength for secure tray removal. The new simplified indirect bonding technique presented here overcomes both these problems.

  11. Human Bond Communication

    DEFF Research Database (Denmark)

    Prasad, Ramjee

    2016-01-01

    Modern dexterous communication technology is progressively enabling humans to communicate their information through them with speech (aural) and media (optical) as underpinning essence. Humans realize this kind of aural and optical information by their optical and auditory senses. However, due...... to certain constraints, the ability to incorporate the other three sensory features namely, olfactory, gustatory, and tactile are still far from reality. Human bond communication is a novel concept that incorporates olfactory, gustatory, and tactile that will allow more expressive and holistic sensory...... information exchange through communication techniques for more human sentiment centric communication. This concept endorses the need of inclusion of other three senses and proposes an innovative approach of holistic communication for future communication network....

  12. 30 CFR 281.33 - Bonds and bonding requirements.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Bonds and bonding requirements. 281.33 Section 281.33 Mineral Resources MINERALS MANAGEMENT SERVICE, DEPARTMENT OF THE INTERIOR OFFSHORE LEASING OF MINERALS OTHER THAN OIL, GAS, AND SULPHUR IN THE OUTER CONTINENTAL SHELF Financial Considerations § 281.33...

  13. 29 CFR 2580.412-19 - Term of the bond, discovery period, other bond clauses.

    Science.gov (United States)

    2010-07-01

    ... SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580.412-19 Term of the bond, discovery... 29 Labor 9 2010-07-01 2010-07-01 false Term of the bond, discovery period, other bond clauses... new bond must be obtained each year. There is nothing in the Act that prohibits a bond for a term...

  14. Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

    Science.gov (United States)

    Zhang, Chun; Feng, Peng; Jiao, Ning

    2013-10-09

    The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

  15. Monte Carlo Codes Invited Session

    International Nuclear Information System (INIS)

    Trama, J.C.; Malvagi, F.; Brown, F.

    2013-01-01

    This document lists 22 Monte Carlo codes used in radiation transport applications throughout the world. For each code the names of the organization and country and/or place are given. We have the following computer codes. 1) ARCHER, USA, RPI; 2) COG11, USA, LLNL; 3) DIANE, France, CEA/DAM Bruyeres; 4) FLUKA, Italy and CERN, INFN and CERN; 5) GEANT4, International GEANT4 collaboration; 6) KENO and MONACO (SCALE), USA, ORNL; 7) MC21, USA, KAPL and Bettis; 8) MCATK, USA, LANL; 9) MCCARD, South Korea, Seoul National University; 10) MCNP6, USA, LANL; 11) MCU, Russia, Kurchatov Institute; 12) MONK and MCBEND, United Kingdom, AMEC; 13) MORET5, France, IRSN Fontenay-aux-Roses; 14) MVP2, Japan, JAEA; 15) OPENMC, USA, MIT; 16) PENELOPE, Spain, Barcelona University; 17) PHITS, Japan, JAEA; 18) PRIZMA, Russia, VNIITF; 19) RMC, China, Tsinghua University; 20) SERPENT, Finland, VTT; 21) SUPERMONTECARLO, China, CAS INEST FDS Team Hefei; and 22) TRIPOLI-4, France, CEA Saclay

  16. Advanced computers and Monte Carlo

    International Nuclear Information System (INIS)

    Jordan, T.L.

    1979-01-01

    High-performance parallelism that is currently available is synchronous in nature. It is manifested in such architectures as Burroughs ILLIAC-IV, CDC STAR-100, TI ASC, CRI CRAY-1, ICL DAP, and many special-purpose array processors designed for signal processing. This form of parallelism has apparently not been of significant value to many important Monte Carlo calculations. Nevertheless, there is much asynchronous parallelism in many of these calculations. A model of a production code that requires up to 20 hours per problem on a CDC 7600 is studied for suitability on some asynchronous architectures that are on the drawing board. The code is described and some of its properties and resource requirements ae identified to compare with corresponding properties and resource requirements are identified to compare with corresponding properties and resource requirements are identified to compare with corresponding properties and resources of some asynchronous multiprocessor architectures. Arguments are made for programer aids and special syntax to identify and support important asynchronous parallelism. 2 figures, 5 tables

  17. Adaptive Markov Chain Monte Carlo

    KAUST Repository

    Jadoon, Khan

    2016-08-08

    A substantial interpretation of electromagnetic induction (EMI) measurements requires quantifying optimal model parameters and uncertainty of a nonlinear inverse problem. For this purpose, an adaptive Bayesian Markov chain Monte Carlo (MCMC) algorithm is used to assess multi-orientation and multi-offset EMI measurements in an agriculture field with non-saline and saline soil. In the MCMC simulations, posterior distribution was computed using Bayes rule. The electromagnetic forward model based on the full solution of Maxwell\\'s equations was used to simulate the apparent electrical conductivity measured with the configurations of EMI instrument, the CMD mini-Explorer. The model parameters and uncertainty for the three-layered earth model are investigated by using synthetic data. Our results show that in the scenario of non-saline soil, the parameters of layer thickness are not well estimated as compared to layers electrical conductivity because layer thicknesses in the model exhibits a low sensitivity to the EMI measurements, and is hence difficult to resolve. Application of the proposed MCMC based inversion to the field measurements in a drip irrigation system demonstrate that the parameters of the model can be well estimated for the saline soil as compared to the non-saline soil, and provide useful insight about parameter uncertainty for the assessment of the model outputs.

  18. Importance iteration in MORSE Monte Carlo calculations

    International Nuclear Information System (INIS)

    Kloosterman, J.L.; Hoogenboom, J.E.

    1994-01-01

    An expression to calculate point values (the expected detector response of a particle emerging from a collision or the source) is derived and implemented in the MORSE-SGC/S Monte Carlo code. It is outlined how these point values can be smoothed as a function of energy and as a function of the optical thickness between the detector and the source. The smoothed point values are subsequently used to calculate the biasing parameters of the Monte Carlo runs to follow. The method is illustrated by an example that shows that the obtained biasing parameters lead to a more efficient Monte Carlo calculation

  19. Monte Carlo approaches to light nuclei

    International Nuclear Information System (INIS)

    Carlson, J.

    1990-01-01

    Significant progress has been made recently in the application of Monte Carlo methods to the study of light nuclei. We review new Green's function Monte Carlo results for the alpha particle, Variational Monte Carlo studies of 16 O, and methods for low-energy scattering and transitions. Through these calculations, a coherent picture of the structure and electromagnetic properties of light nuclei has arisen. In particular, we examine the effect of the three-nucleon interaction and the importance of exchange currents in a variety of experimentally measured properties, including form factors and capture cross sections. 29 refs., 7 figs

  20. Monte Carlo approaches to light nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, J.

    1990-01-01

    Significant progress has been made recently in the application of Monte Carlo methods to the study of light nuclei. We review new Green's function Monte Carlo results for the alpha particle, Variational Monte Carlo studies of {sup 16}O, and methods for low-energy scattering and transitions. Through these calculations, a coherent picture of the structure and electromagnetic properties of light nuclei has arisen. In particular, we examine the effect of the three-nucleon interaction and the importance of exchange currents in a variety of experimentally measured properties, including form factors and capture cross sections. 29 refs., 7 figs.

  1. Importance iteration in MORSE Monte Carlo calculations

    International Nuclear Information System (INIS)

    Kloosterman, J.L.; Hoogenboom, J.E.

    1994-02-01

    An expression to calculate point values (the expected detector response of a particle emerging from a collision or the source) is derived and implemented in the MORSE-SGC/S Monte Carlo code. It is outlined how these point values can be smoothed as a function of energy and as a function of the optical thickness between the detector and the source. The smoothed point values are subsequently used to calculate the biasing parameters of the Monte Carlo runs to follow. The method is illustrated by an example, which shows that the obtained biasing parameters lead to a more efficient Monte Carlo calculation. (orig.)

  2. Monte carlo simulation for soot dynamics

    KAUST Repository

    Zhou, Kun

    2012-01-01

    A new Monte Carlo method termed Comb-like frame Monte Carlo is developed to simulate the soot dynamics. Detailed stochastic error analysis is provided. Comb-like frame Monte Carlo is coupled with the gas phase solver Chemkin II to simulate soot formation in a 1-D premixed burner stabilized flame. The simulated soot number density, volume fraction, and particle size distribution all agree well with the measurement available in literature. The origin of the bimodal distribution of particle size distribution is revealed with quantitative proof.

  3. O hydrogen bonds in alkaloids

    Indian Academy of Sciences (India)

    An overview of general classification scheme, medicinal importance and crystal structure analysis with emphasis on the role of hydrogen bonding in some alkaloids is presented in this paper. The article is based on a general kind of survey while crystallographic analysis and role of hydrogen bonding are limited to only ...

  4. Distance criterion for hydrogen bond

    Indian Academy of Sciences (India)

    First page Back Continue Last page Overview Graphics. Distance criterion for hydrogen bond. In a D-H ...A contact, the D...A distance must be less than the sum of van der Waals Radii of the D and A atoms, for it to be a hydrogen bond.

  5. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    2012-01-01

    of the article is to provide possible explanations for the puzzle of why small retail investors hold structured bonds. The investment universe consists of a stock index, a risk-free bank account, and a structured bond containing an option written on another index. We apply expected utility maximization...

  6. Fusion-bonded fluidic interconnects

    NARCIS (Netherlands)

    Fazal, I.; Elwenspoek, Michael Curt

    2008-01-01

    A new approach to realize fluidic interconnects based on the fusion bonding of glass tubes with silicon is presented. Fusion bond strength analyses have been carried out. Experiments with plain silicon wafers and coated with silicon oxide and silicon nitride are performed. The obtained results are

  7. SOCIAL BONDING: REGULATION BY NEUROPEPTIDES

    Directory of Open Access Journals (Sweden)

    Claudia eLieberwirth

    2014-06-01

    Full Text Available Affiliative social relationships (e.g., among spouses, family members, and friends play an essential role in human society. These relationships affect psychological, physiological, and behavioral functions. As positive and enduring bonds are critical for the overall well-being of humans, it is not surprising that considerable effort has been made to study the neurobiological mechanisms that underlie social bonding behaviors. The present review details the involvement of the nonapeptides, oxytocin (OT and arginine vasopressin (AVP, in the regulation of social bonding in mammals including humans. In particular, we will discuss the role of OT and AVP in the formation of social bonds between partners of a mating pair as well as between parents and their offspring. Furthermore, the role of OT and AVP in the formation of interpersonal bonding involving trust is also discussed.

  8. Fusion-bonded fluidic interconnects

    International Nuclear Information System (INIS)

    Fazal, I; Elwenspoek, M C

    2008-01-01

    A new approach to realize fluidic interconnects based on the fusion bonding of glass tubes with silicon is presented. Fusion bond strength analyses have been carried out. Experiments with plain silicon wafers and coated with silicon oxide and silicon nitride are performed. The obtained results are discussed in terms of the homogeneity and strength of fusion bond. High pressure testing shows that the bond strength is large enough for most applications of fluidic interconnects. The bond strength for 525 µm thick silicon, with glass tubes having an outer diameter of 6 mm and with a wall thickness of 2 mm, is more than 60 bars after annealing at a temperature of 800 °C

  9. Sibling bereavement and continuing bonds.

    Science.gov (United States)

    Packman, Wendy; Horsley, Heidi; Davies, Betty; Kramer, Robin

    2006-11-01

    Historically, from a Freudian and medical model perspective, emotional disengagement from the deceased was seen as essential to the successful adaptation of bereavement. A major shift in the bereavement literature has occurred and it is now generally accepted that despite the permanence of physical separation, the bereaved remains involved and connected to the deceased and can be emotionally sustained through continuing bonds. The majority of literature has focused on adults and on the nature of continuing bonds following the death of a spouse. In this article, the authors demonstrate how the continuing bonds concept applies to the sibling relationship. We describe the unique continued relationship formed by bereaved children and adolescents following a sibling loss, highlight the factors that influence the siblings continuing bonds expressions, and offer clinical interventions. In our view, mental health professionals can play an important role in helping parents encourage activities that may facilitate the creation and maintenance of continuing bonds in their children.

  10. Microbial adhesion on novel yttria-stabilized tetragonal zirconia (Y-TZP) implant surfaces with nitrogen-doped hydrogenated amorphous carbon (a-C:H:N) coatings.

    Science.gov (United States)

    Schienle, Stefanie; Al-Ahmad, Ali; Kohal, Ralf Joachim; Bernsmann, Falk; Adolfsson, Erik; Montanaro, Laura; Palmero, Paola; Fürderer, Tobias; Chevalier, Jérôme; Hellwig, Elmar; Karygianni, Lamprini

    2016-09-01

    Biomaterial surfaces are at high risk for initial microbial colonization, persistence, and concomitant infection. The rationale of this study was to assess the initial adhesion on novel implant surfaces of Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans upon incubation. The tested samples were 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) samples with nitrogen-doped hydrogenated amorphous carbon (a-C:H:N) coating (A) and 3Y-TZP samples coated with ceria-stabilized zirconia-based (Ce-TZP) composite and a-C:H:N (B). Uncoated 3Y-TZP samples (C) and bovine enamel slabs (BES) served as controls. Once the surface was characterized, the adherent microorganisms were quantified by estimating the colony-forming units (CFUs). Microbial vitality was assessed by live/dead staining, and microbial-biomaterial surface topography was visualized by scanning electron microscopy (SEM). Overall, A and B presented the lowest CFU values for all microorganisms, while C sheltered significantly less E. faecalis, P. aeruginosa, and C. albicans than BES. Compared to the controls, B demonstrated the lowest vitality values for E. coli (54.12 %) and C. albicans (67.99 %). Interestingly, A (29.24 %) exhibited higher eradication rates for S. aureus than B (13.95 %). Within the limitations of this study, a-C:H:N-coated 3Y-TZP surfaces tended to harbor less initially adherent microorganisms and selectively interfered with their vitality. This could enable further investigation of the new multi-functional zirconia surfaces to confirm their favorable antimicrobial properties in vivo.

  11. Estimation of lower flammability limits of C-H compounds in air at atmospheric pressure, evaluation of temperature dependence and diluent effect.

    Science.gov (United States)

    Mendiburu, Andrés Z; de Carvalho, João A; Coronado, Christian R

    2015-03-21

    Estimation of the lower flammability limits of C-H compounds at 25 °C and 1 atm; at moderate temperatures and in presence of diluent was the objective of this study. A set of 120 C-H compounds was divided into a correlation set and a prediction set of 60 compounds each. The absolute average relative error for the total set was 7.89%; for the correlation set, it was 6.09%; and for the prediction set it was 9.68%. However, it was shown that by considering different sources of experimental data the values were reduced to 6.5% for the prediction set and to 6.29% for the total set. The method showed consistency with Le Chatelier's law for binary mixtures of C-H compounds. When tested for a temperature range from 5 °C to 100 °C, the absolute average relative errors were 2.41% for methane; 4.78% for propane; 0.29% for iso-butane and 3.86% for propylene. When nitrogen was added, the absolute average relative errors were 2.48% for methane; 5.13% for propane; 0.11% for iso-butane and 0.15% for propylene. When carbon dioxide was added, the absolute relative errors were 1.80% for methane; 5.38% for propane; 0.86% for iso-butane and 1.06% for propylene. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Palladium-Catalyzed Direct C-H Arylations of Dioxythiophenes Bearing Reactive Functional Groups: A Step-Economical Approach for Functional π-Conjugated Oligoarenes

    KAUST Repository

    Liu, Ching-Yuan

    2015-06-25

    A Pd-catalyzed and single-step C-H arylation of dioxythiophene derivates bearing unprotected reactive functional groups (-OH, -COOH, -N3) in a phosphine-free manner has been developed. Various dioxythiopene-based oligoarenes with extended π-conjugation are obtained with good yields (up to 90%). These oligoarenes display suitable optical properties (absorption and emission maxima, quantum yields) and contain reactive functional groups suitable for further conjugations with bioactive molecules. This new methodology is step economical (fewer synthetic steps), environmental friendly (no toxic metal-containing side-poducts) and the oligoarenes synthesized are potentially applicable for bio-labeling, bioimaging, and biosensing.

  13. Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary.

    Science.gov (United States)

    Yao, Qi-Jun; Zhang, Shuo; Zhan, Bei-Bei; Shi, Bing-Feng

    2017-06-01

    Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination.

    Science.gov (United States)

    Bera, Milan; Maji, Arun; Sahoo, Santosh K; Maiti, Debabrata

    2015-07-13

    Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium-catalyzed synthesis of divinylbenzenes by meta-C-H olefination of sulfone-based arenes. Successful sequential olefinations in a position-selective manner provided a novel route for the synthesis of hetero-dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5-trialkenylated compounds can be generated upon successful removal of the directing group. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Palladium-Catalyzed Direct C-H Arylations of Dioxythiophenes Bearing Reactive Functional Groups: A Step-Economical Approach for Functional π-Conjugated Oligoarenes

    KAUST Repository

    Liu, Ching-Yuan; Chong, Hui; Lin, Hsing-An; Yamashita, Yoshiro; Zheng, Bin; Huang, Kuo-Wei; Hashizume, Daisuke; Yu, Hsiao-hua

    2015-01-01

    A Pd-catalyzed and single-step C-H arylation of dioxythiophene derivates bearing unprotected reactive functional groups (-OH, -COOH, -N3) in a phosphine-free manner has been developed. Various dioxythiopene-based oligoarenes with extended π-conjugation are obtained with good yields (up to 90%). These oligoarenes display suitable optical properties (absorption and emission maxima, quantum yields) and contain reactive functional groups suitable for further conjugations with bioactive molecules. This new methodology is step economical (fewer synthetic steps), environmental friendly (no toxic metal-containing side-poducts) and the oligoarenes synthesized are potentially applicable for bio-labeling, bioimaging, and biosensing.

  16. Structure phenomena in the bond zone of explosively bonded plates

    International Nuclear Information System (INIS)

    Livne, Z.

    1979-12-01

    In the bond areas of couples of explosively bonded plates, there are often zones, generally designated as ''molten pockets'', which have undergone melting and solidification. The object of the present study was to investigate molten pockets, which have a decisive effect on bond quality. The experimental samples for the study were chosen in consideration of the mutual behaviour of the plates constituting the couples, according to their equilibrium phase diagrams. To facilitate the investigation, large plates were bonded under conditions that enabled to to obtain wavy bond zones that included relatively large molten pockets. To clarify the complex nature of molten pockets and their surroundings, a wide variety of methods were employed. It was found that the shape and composition of molten pockets largely depend upon the mechanism of formation of both the bond wave and the molten pockets. It was also found that the composition of molten pockets is not homogeneous, which is manifest in the modification of the composition of the pockets, the solidification morphology, the phases, which have been identified by X-ray diffraction, and the bond strenght and hardness. Moreover, the different solidification morphologies revealed by metallography were found to depend upon the types of plates bonded, the bonding conditions and the location of pockets in the wavy interface. For molten pockets, cooling rates of 10 4 to 10 5 (degC/sec) have been deduced from interdendritic spacing, and found to be in good agreement with calculations after a mathematical model. It seems that the fast cooling rates and the steep temperature gradients are at the origin of the particular solidification phenomena observed in molten pockets

  17. Dentin-bonding agents

    Directory of Open Access Journals (Sweden)

    João Carlos Gomes

    2008-01-01

    Full Text Available New dental restorative materials have been developed to meet not only the functional demands, but esthetics as well, and in the last few years an enormous range of new materials has appeared for use in dentistry. Among them, several adhesive systems, and different operative techniques for each group materials. Therefore, is indispensable for the professional to know about the properties, characteristics, and association of these materials with the dental structures, in order to select and use them correctly. Should conventional self-etching adhesive systems be used? This question encouraged this literature review to be conducted, with the aim of comparing the conventional adhesive systems with the self-etching systems and to look for scientific data that would help professionals to choose which adhesive system to use. When compared to conventional systems, it was noted that the self-etching systems show less sensitivity to technique, especially as regards errors the operator could commit. The self-etching systems, particularly the 2-step type, have shown equivalent values of bond strength, marginal microleakage and performance, therefore, will be an option for direct composite resin restorations in posterior teeth.

  18. 11th International Conference on Monte Carlo and Quasi-Monte Carlo Methods in Scientific Computing

    CERN Document Server

    Nuyens, Dirk

    2016-01-01

    This book presents the refereed proceedings of the Eleventh International Conference on Monte Carlo and Quasi-Monte Carlo Methods in Scientific Computing that was held at the University of Leuven (Belgium) in April 2014. These biennial conferences are major events for Monte Carlo and quasi-Monte Carlo researchers. The proceedings include articles based on invited lectures as well as carefully selected contributed papers on all theoretical aspects and applications of Monte Carlo and quasi-Monte Carlo methods. Offering information on the latest developments in these very active areas, this book is an excellent reference resource for theoreticians and practitioners interested in solving high-dimensional computational problems, arising, in particular, in finance, statistics and computer graphics.

  19. Quantum Monte Carlo approaches for correlated systems

    CERN Document Server

    Becca, Federico

    2017-01-01

    Over the past several decades, computational approaches to studying strongly-interacting systems have become increasingly varied and sophisticated. This book provides a comprehensive introduction to state-of-the-art quantum Monte Carlo techniques relevant for applications in correlated systems. Providing a clear overview of variational wave functions, and featuring a detailed presentation of stochastic samplings including Markov chains and Langevin dynamics, which are developed into a discussion of Monte Carlo methods. The variational technique is described, from foundations to a detailed description of its algorithms. Further topics discussed include optimisation techniques, real-time dynamics and projection methods, including Green's function, reptation and auxiliary-field Monte Carlo, from basic definitions to advanced algorithms for efficient codes, and the book concludes with recent developments on the continuum space. Quantum Monte Carlo Approaches for Correlated Systems provides an extensive reference ...

  20. Monte Carlo simulations for plasma physics

    International Nuclear Information System (INIS)

    Okamoto, M.; Murakami, S.; Nakajima, N.; Wang, W.X.

    2000-07-01

    Plasma behaviours are very complicated and the analyses are generally difficult. However, when the collisional processes play an important role in the plasma behaviour, the Monte Carlo method is often employed as a useful tool. For examples, in neutral particle injection heating (NBI heating), electron or ion cyclotron heating, and alpha heating, Coulomb collisions slow down high energetic particles and pitch angle scatter them. These processes are often studied by the Monte Carlo technique and good agreements can be obtained with the experimental results. Recently, Monte Carlo Method has been developed to study fast particle transports associated with heating and generating the radial electric field. Further it is applied to investigating the neoclassical transport in the plasma with steep gradients of density and temperatures which is beyong the conventional neoclassical theory. In this report, we briefly summarize the researches done by the present authors utilizing the Monte Carlo method. (author)