2,034 research outputs found

    Electrochemical Preparation and Applications of Copper(I) Acetylides: A Demonstration of How Electrochemistry Can Be Used to Facilitate Sustainability in Homogeneous Catalysis

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    Copper(I) acetylides are important intermediates for many syntheses and have been prepared here electrochemically in an energy efficient manner. These were subsequently employed in simple organic C–C bond forming reactions. We also demonstrate that application of Faraday's laws allows the charge to be calculated so that only the required amount of metal is used. In addition, the application of copper-coated graphite electrodes allows the maximum atom efficiency for this process and even offers a recovery strategy to extract the metal following completion of the reaction

    Investigations Into the Mechanism of Copper-Mediated Glaser-Hay Couplings Using Electrochemical Techniques

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    The mechanism of the copper mediated C-C bond forming reaction known as Glaser-Hay coupling (alkyne dimerization) has been investigated using electrochemical techniques. Applying an oxidative potential to a copper or copper-coated graphite electrode in the presence of the organic base DABCO results in the dimerization of phenylacetylene in good yield. Further mechanistic investigation has shown that this reaction medium results in the assembly of a dinuclear Cu(I) complex which, although previously reported, has never been shown to have catalytic properties for C-C bond formation. The complex is reminiscent of that proposed in the Bohlmann model for the Glaser-Hay reaction and as such lends weight to this proposed mechanism above the alternative proposed mononuclear catalytic cycle

    D1 receptors in the nucleus accumbens-shell, but not the core, are involved in mediating ethanol-seeking behavior of alcohol-preferring (P) rats

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    Clinical and preclinical research suggest that activation of the mesolimbic dopamine (DA) system is involved in mediating the rewarding actions of drugs of abuse, as well as promoting drug-seeking behavior. Inhibition of DA D1 receptors in the nucleus accumbens (Acb) can reduce ethanol (EtOH)-seeking behavior of non-selective rats triggered by environmental context. However, to date, there has been no research on the effects of D1 receptor agents on EtOH- seeking behavior of high alcohol-preferring (P) rats following prolonged abstinence. The objective of the present study was to examine the effects of microinjecting the D1 antagonist SCH 23390 or the D1 agonist A-77636 into the Acb shell or Acb core on spontaneous recovery of EtOH-seeking behavior. After 10 weeks of concurrent access to EtOH and water, P rats underwent seven extinction sessions (EtOH and water withheld), followed by 2 weeks in their home cages without access to EtOH or operant sessions. In the 2nd week of the home cage phase, rats were bilaterally implanted with guide cannula aimed at the Acb shell or Acb core; rats were allowed 7d ays to recover before EtOH-seeking was assessed by the Pavlovian Spontaneous Recovery (PSR) model. Administration of SCH23390 (1ÎĽg/side) into the Acb shell inhibited responding on the EtOH lever, whereas administration of A-77636 (0.125ÎĽg/side) increased responding on the EtOH lever. Microinfusion of D1 receptor agents into the Acb core did not alter responding on the EtOH lever. Responses on the water lever were not altered by any of the treatments. The results suggest that activation of D1 receptors within the Acb shell, but not Acb core, are involved in mediating PSR of EtOH-seeking behavior of P rats

    Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide-Extraction Properties and Metal Ion Speciation in Bis-1,2,4-Triazine Ligands

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    Calling all actinides! Bis-1,2,4-triazine ligands bearing five-membered rings were synthesized and evaluated as actinide-selective extractants. Tuning the size of the aliphatic ring leads to subtle changes in actinide-extraction properties. The origins of these changes were elucidated at the molecular level, paving the way for the rational design of improved actinide-selective extractants for reprocessing of spent nuclear fuel., The synthesis and evaluation of three novel bis-1,2,4-triazine ligands containing five-membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1–3 containing six-membered aliphatic rings, the distribution ratios for relevant f-block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of AmIII and CmIII from nitric acid. The speciation of the ligands with trivalent f-block metal ions was probed using NMR titrations and competition experiments, time-resolved laser fluorescence spectroscopy and X-ray crystallography. While the tetradentate ligands 8 and 10 formed LnIII^{III} complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3, significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10. The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with YIII^{III}, LuIII^{III} and PrIII^{III} are very similar to those formed by 2 and 3 with LnIII^{III}. Ligand 10 forms CmIII^{III} and EuIII^{III} 1:2 complexes that are thermodynamically less stable than those formed by ligand 3, suggesting that less hydrophobic ligands form less stable AnIII^{III} complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity

    Comprehension as social and intellectual practice: Rebuilding curriculum in low socioeconomic and cultural minority schools

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    This article reframes the concept of comprehension as a social and intellectual practice. It reviews current approaches to reading instruction for linguistically and culturally diverse and low socioeconomic students, noting an emphasis on comprehension as autonomous skills. The Four Resources model (Freebody & Luke, 1990) is used to make the case for the integration of comprehension instruction with an emphasis on student cultural and community knowledge, and substantive intellectual and sociocultural content in elementary school curricula. Illustrations are drawn from research underway on the teaching of literacy in primary schools in low SES communities

    Gamma and pulsed electron radiolysis studies of CyMe4BTBP and CyMe4BTPhen: Identification of radiolysis products and effects on the hydrometallurgical separation of trivalent actinides and lanthanides

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    The radiolytic stability of the highly selective ligands CyMe4BTBP and CyMe4BTPhen against ionizing gamma radiation was studied in 1-octanol solution. CyMe4BTBP and CyMe4BTPhen are important extractants for a potential treatment of used nuclear fuel. They were studied under identical experimental conditions to directly compare the effects of gamma and pulsed electron radiolysis on the ligands and systematically study the influence of structural changes in the ligand backbone. Distribution ratios of Am3+, Cm3+ and Eu3+, the residual concentration of CyMe4BTBP and CyMe4BTPhen in solution, and the formation of radiolysis products were studied as a function of absorbed gamma dose and presence of an acidic aqueous phase during irradiation. Quantitative and semi-quantitative analyses were used to elucidate the radiolysis mechanism for both ligands. Addition products of alpha-hydroxyoctyl radicals formed through radiolysis of the 1-octanol diluent to the ligand molecules were identified as the predominant radiolysis products. These addition products also extract trivalent metal ions, as distribution ratios remained high although the parent molecule concentrations decreased. Therefore, the utilization time of a solvent using these extractants under the harsh conditions of used nuclear fuel treatment could be considerably longer than expected. Understanding the radiolysis mechanism is crucial for designing more radiation resistant extractants

    Pre-main-sequence Lithium Depletion

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    In this review I briefly discuss the theory of pre-main-sequence (PMS) Li depletion in low-mass (0.075<M<1.2 Msun) stars and highlight those uncertain parameters which lead to substantial differences in model predictions. I then summarise observations of PMS stars in very young open clusters, clusters that have just reached the ZAMS and briefly highlight recent developments in the observation of Li in very low-mass PMS stars.Comment: 8 pages, invited review at "Chemical abundances and mixing in stars in the Milky Way and its satellites", eds. L. Pasquini, S. Randich. ESO Astrophysics Symposium (Springer-Verlag

    An overview of solvent extraction processes developed in Europe for advanced nuclear fuel recycling, Part 2 — homogeneous recycling

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    The hydrometallurgical separation concepts for the recycling of irradiated nuclear fuels developed in Europe are presented and discussed. Whilst Part 1 of the review focused on concepts for heterogeneous recycling of minor actinides, this article focuses on group recycling of transuranic actinides, which would support homogeneous recycling scenarios. Most of these concepts were developed within European collaborative projects and involve solvent extraction processes separating all the actinides (U-Cm) in two cycles. The first cycle uses a monoamide extractant to recover uranium leaving all the transuranic actinides in the aqueous raffinate with the fission products. The second cycle aims for a group recovery of the transuranium elements and several strategies have been proposed for this stage. In this review article, the various solvent extraction processes are summarised and the key features of the process schemes are compared

    Diffusion in supersonic, turbulent, compressible flows

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    We investigate diffusion in supersonic, turbulent, compressible flows. Supersonic turbulence can be characterized as network of interacting shocks. We consider flows with different rms Mach numbers and where energy necessary to maintain dynamical equilibrium is inserted at different spatial scales. We find that turbulent transport exhibits super-diffusive behavior due to induced bulk motions. In a comoving reference frame, however, diffusion behaves normal and can be described by mixing length theory extended into the supersonic regime.Comment: 11 pages, incl. 5 figures, accepted for publication in Physical Review E (a high-resolution version is available at http://www.aip.de./~ralf/Publications/p21.abstract.html

    Time invaders:conceptualizing performative game time

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    This chapter characterizes framing devices and other game elements as unstable signifiers, evaluating performances according to how they generate diachronic or synchronic effects by acting on those signifiers. Videogames make use of computers’ capabilities to present a very large set of these signifiers and thus generate highly complex forms of temporal experience. Because neither diachrony (exemplified by player performance) nor synchrony (computer-coded rule structures) can complete their respective operations and always leave a differential margin, videogames can be understood as diachrono-synchronic systems.Performative multiplicities of various sizes can be analyzed in terms of how they draw together or separate performances, creating a comparative methodology for describing temporal experience in videogames. One of the key synchronic effects is the Game Over, which has a high-level effect on all performances of a game. Considered as a synchronic horizon of experience, the Game Over provides a concept capable of addressing the heterogeneous and composite set of videogame elements in terms of how players interpret unstable signifiers. This includes narrative, which can be rigorously defined in terms of its synchronizing effect on a game’s performative multiplicity
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