8,767 research outputs found

    Hyperonic mixing in five-baryon double-strangeness hypernuclei in a two-channel treatment

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    Properties of hypernuclei ΛΛ5_{\Lambda \Lambda}^5H and ΛΛ5_{\Lambda \Lambda }^5He are studied in a two-channel approach with explicit treatment of coupling of channels ^3\text{Z}+\Lambda+\Lambda and \alpha+\Xi. Diagonal \Lambda\Lambda and coupling \Lambda\Lambda-\Xi N interactions are derived within G-matrix procedure from Nijmegen meson-exchange models. Bond energy \Delta B_{\Lambda\Lambda} in ΛΛ5_{\Lambda \Lambda}^5He exceeds significantly that in ΛΛ5_{\Lambda \Lambda}^5H due to the channel coupling. Diagonal \Xi\alpha attraction amplifies the effect, which is sensitive also to \Lambda-core interaction. The difference of the \Delta B_{\Lambda\Lambda} values can be an unambiguous signature of the \Lambda\Lambda-\Xi N coupling in \Lambda\Lambda hypernuclei. However, improved knowledge of the hyperon-nucleus potentials is needed for quantitative extraction of the coupling strength from future data on the \Lambda\Lambda hypernuclear binding energies.Comment: 11 pages with 3 figures; Phys. Rev. C, accepte

    Fate of the Bose insulator in the limit of strong localization and low Cooper-pair density in ultrathin films

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    A Bose insulator composed of a low density of strongly localized Cooper pairs develops at the two-dimensional superconductor to insulator transition (SIT) in a number of thin film systems. Investigations of ultrathin amorphous PbBi films far from the SIT described here provide evidence that the Bose insulator gives way to a second insulating phase with decreasing film thickness. At a critical film thickness dc the magnetoresistance changes sign from positive, as expected for boson transport, to negative, as expected for fermion transport, signs of local Cooper-pair phase coherence effects on transport vanish, and the transport activation energy exhibits a kink. Below dc pairing fluctuation effects remain visible in the high-temperature transport while the activation energy continues to rise. These features show that Cooper pairing persists and suggest that the localized unpaired electron states involved in transport are interspersed among regions of strongly localized Cooper pairs in this strongly localized, low Cooper-pair density phase

    Clone Detection and Elimination for Haskell

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    Duplicated code is a well known problem in software maintenance and refactoring. Code clones tend to increase program size and several studies have shown that duplicated code makes maintenance and code understanding more complex and time consuming. This paper presents a new technique for the detection and removal of duplicated Haskell code. The system is implemented within the refactoring framework of the Haskell Refactorer (HaRe), and uses an Abstract Syntax Tree (AST) based approach. Detection of duplicate code is automatic, while elimination is semi-automatic, with the user managing the clone removal. After presenting the system, an example is given to show how it works in practice

    Observation of giant positive magnetoresistance in a Cooper pair insulator.

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    Ultrathin amorphous Bi films, patterned with a nanohoneycomb array of holes, can exhibit an insulating phase with transport dominated by the incoherent motion of Cooper pairs (CP) of electrons between localized states. Here, we show that the magnetoresistance (MR) of this Cooper pair insulator (CPI) phase is positive and grows exponentially with decreasing temperature T, for T well below the pair formation temperature. It peaks at a field estimated to be sufficient to break the pairs and then decreases monotonically into a regime in which the film resistance assumes the T dependence appropriate for weakly localized single electron transport. We discuss how these results support proposals that the large MR peaks in other unpatterned, ultrathin film systems disclose a CPI phase and provide new insight into the CP localization

    Alkali-metal-mediated zincation (AMMZn) meets N-heterocyclic carbene (NHC) chemistry : Zn–H exchange reactions and structural authentication of a dinuclear Au(I) complex with a NHC anion

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    Merging two evolving areas in synthesis, namely cooperative bimetallics and N-heterocyclic carbenes (NHCs), this study reports the isolation of the first intermediates of alkali-metal-mediated zincation (AMMZn) of a free NHC and a Zn–NHC complex using sodium zincate [(TMEDA)NaZn(TMP)(tBu)2] (1) as a metallating reagent. The structural authentication of (THF)3Na[:C{[N(2,6-iPr2C6H3)]2CHCZn(tBu2)}] (2) and [Na(THF)6]+[tBu2Zn:C{[N(2,6-iPr2C6H3)]2CHCZn(tBu2)}]− (4), resulting from the reactions of 1 with unsaturated free NHC IPr (IPr = 1,3-bis(2,6-di-isopropylphenylimidazole-2-ylidene) and NHC complex ZntBu2IPr (3) respectively demonstrates that in both cases, this mixed-metal approach can easily facilitate the selective C4 zincation of the unsaturated backbone of the NHC ligand. Furthermore, the generation of anionic NHC fragments enables dual coordination through their normal (C2) and abnormal (C4) positions to the bimetallic system, stabilising the kinetic AMMZn intermediates which normally go undetected and provides new mechanistic insights in to how these mixed-metal reagents operate. In stark contrast to this bimetallic approach when NHC-complex 3 is reacted with a more conventional single-metal base such as tBuLi, the deprotonation of the coordinated carbene is inhibited, favouring instead, co-complexation to give NHC-stabilised [IPr·LiZntBu3] (5). Showing the potential of 2 to act as a transfer agent of its anionic NHC unit to transition metal complexes, this intermediate reacts with two molar equivalents of [ClAu(PPh3)] to afford the novel digold species [ClAu:C{[N(2,6-iPr2C6H3)]2CHCAu(PPh3)}] (6) resulting from an unprecedented double transmetallation reaction which involves the simultaneous exchange of both cationic (Na+) and neutral (ZntBu2) entities on the NHC framework

    Conformations of N-Heterocyclic Carbene Ligands in Ruthenium Complexes Relevant to Olefin Metathesis

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    The structure of ruthenium-based olefin metathesis catalyst 3 and model π-complex 5 in solution and in the solid state are reported. The N-tolyl ligands, due to their lower symmetry than the traditional N-mesityl substituents, complicate this analysis, but ultimately provide explanation for the enhanced reactivity of 3 relative to standard catalyst 2. The tilt of the N-tolyl ring provides additional space near the ruthenium center, which is consistent with the enhanced reactivity of 3 toward sterically demanding substrates. Due to this tilt, the more sterically accessible face bears the two methyl substituents of the N-aryl rings. These experimental studies are supported by computational studies of these complexes by DFT. The experimental data provides a means to validate the accuracy of the B3LYP and M06 functionals. B3LYP provides geometries that match X-ray crystal structural data more closely, though it leads to slightly less (0.5 kcal mol^(−1)) accuracy than M06 most likely because it underestimates attractive noncovalent interactions

    Variable coordination of amine functionalised N-heterocyclic carbene ligands to Ru, Rh and Rr: C-H and N-H activation and catalytic transfer hydrogenation

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    Chelating amine and amido complexes of late transition metals are highly valuable bifunctional catalysts in organic synthesis, but complexes of bidentate amine–NHC and amido–NHC ligands are scarce. Hence, we report the reactions of a secondary-amine functionalised imidazolium salt 2a and a primary-amine functionalised imidazolium salt 2b with [( p -cymene)RuCl 2 ] 2 and [Cp*MCl 2 ] 2 (M = Rh, Ir). Treating 2a with [Cp*MCl 2 ] 2 and NaOAc gave the cyclometallated compounds Cp*M(C,C)I (M = Rh, 3 ;M = Ir, 4 ), resulting from aromatic C–H activation. In contrast, treating 2b with [( p -cymene)RuCl 2 ] 2 ,Ag 2 O and KI gave the amine–NHC complex [( p -cymene)Ru(C,NH 2 )I]I ( 5 ). The reaction of 2b with [Cp*MCl 2 ] 2 (M = Rh, Ir), NaO t Bu and KI gave the amine–NHC complex [Cp*Rh(NH 2 )I]I ( 6 ) or the amido–NHC complex Cp*Ir(C,NH)I ( 7 ); both protonation states of the Ir complex could be accessed: treating 7 with trifluoroacetic acid gave the amine–NHC complex [Cp*Ir(C,NH 2 )I][CF 3 CO 2 ]( 8 ). These are the first primary amine– or amido–NHC complexes of Rh and Ir. Solid-state structures of the complexes 3–8 have been determined by single crystal X-ray diffraction. Complexes 5 , 6 and 7 are pre-catalysts for the catalytic transfer hydrogenation of acetophenone to 1-phenylethanol, with ruthenium complex 5 demonstrating especially high reactivity

    Designing organometallic compounds for catalysis and therapy

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    Bioorganometallic chemistry is a rapidly developing area of research. In recent years organometallic compounds have provided a rich platform for the design of effective catalysts, e.g. for olefin metathesis and transfer hydrogenation. Electronic and steric effects are used to control both the thermodynamics and kinetics of ligand substitution and redox reactions of metal ions, especially Ru II. Can similar features be incorporated into the design of targeted organometallic drugs? Such complexes offer potential for novel mechanisms of drug action through incorporation of outer-sphere recognition of targets and controlled activation features based on ligand substitution as well as metal- and ligand-based redox processes. We focus here on η 6-arene, η 5-cyclopentadienyl sandwich and half-sandwich complexes of Fe II, Ru II, Os II and Ir III with promising activity towards cancer, malaria, and other conditions. © 2012 The Royal Society of Chemistry

    The complex binder based on Portland cement andash-and-slag wastes from thermal power stations

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    Increase in the balance of boiler and furnace fuel of the energy sector of the Republic of Belarus the proportion of own energy resources (milling peat and wood chips) places priority on resolving the issues of utilization of ash-and-slag wastes and reducing the area of ash-and-slag disposal sites, which cause irreparable damage to the environment. A considerable amount of research has been devoted to the utilization of ash-and-slag wastes. There are more than 300 technologies of their recycling and use. Ash and slag wastes are used in the production of concrete, mortars, ceramics, heat and water insulating materials, road construction. The world experience shows the potential of 70-80% utilization of ash and slag, as, for example, in some European countries. However, the cost of the recycling of ash-and-slag wastes with the production and simultaneous neutralization of wastes can be higher than the cost of the production. One of the directions of the use of ash and slag wastes is the production on their basis of new types of complex binder that have increased strength and low prime cost. The replacement of a part of cement with active mineral additive allows to achieve significant saving of binder. The existing methods of the production of complex binders include the stages of joint or separate grinding of cement clinker and mineral additive with following mixing. Significant energy costs for grinding increase the cost of binder. In this regard, the development of the effective complex binder with the use of ash-and-slag wastes of the Belarussian state district power station in Orekhovsk using resource-saving technology is the actual research objective
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