556 research outputs found

    Nucleophilic substitution and cyclisation reactions of some polyfluoro-heteroaromatic and polyfluoroaromatic compounds

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    This thesis describes the reactions of some highly fluorinated aromatic and heteroaromatic compounds, in particular derivatives of naphthalene, quinoline and isoquinoline. Chapter 1 provides a general introduction to the preparation, reactions and applications of fluorine containing organic materials. Chapter 2 describes the reactions of some quinoline- and isoquinoline- thiolates with dimethyl acetylenedicarboxylate in an attempt to form six membered heterocycles. Chapter 3 describes nucleophilic substitution reactions of heptafluoro- quinoline and -isoquinoline with sulphur and oxygen nucleophiles. The sulphur nucleophiles are found to attack the 6- site in the isoquinoline and the 4- site in the quinoline. The oxygen nucleophiles attack the 1- site in the isoquinoline and 2- and 4- sites in the quinoline. Chapter 4 describes competition experiments of heptafluoro-quinoline and -isoquinoline with nucleophiles. Relative rates of attack at the 1- position and 6- position in the isoquinoline are determined for a variety of nucleophiles. The relative rates of two nucleophiles are determined for 4- attack in the quinoline. The relative reactivities of the two heterocycles are determined for two different nucleophiles. Chapter 5 describes the pyrolysis of heptafluoro-2-naphtiiyl propynoate which yield two difluoro-butenone derivatives. These decarbonylate under further pyrolysis to yield a 1,1-difluorocyclopropene. All the products were identified by X-ray crystallography. Chapter 6 gives experimental details for Chapter 2 to Chapter 5

    Nikolai Evreinov and Edith Craig as Mediums of Modernist Sensibility

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    Nikolai Evreinov (1870-1953) was a Russian playwright, director, and theorist of the theatre who played a leading part in the modernist movement of Russian theatre. Evreinov's 1911 monodrama The Theatre of the Soul (V kulisakh dushi) was staged by the Crooked Mirror theatre in St Petersburg in 1912. It was also performed in London (1915) and Rome (1929), and inspired Man Ray to create his aerograph The Theatre of the Soul (1917). In this article Alexandra Smith links Evreinov's play to Russian modernist thought shaped by the atmosphere of crisis associated with the Russo-Japanese War and the first Russian Revolution. It demonstrates that Edith Craig's production of Evreinov's play suggests that the philosophy of theatricalization of everyday life might enable modern subjects to overcome the fragmentation of modern society. Craig's use of the montage-like techniques of Evreinov's play prefigures cinematographic experiments of the 1920s and Marinetti's notion of synthetic theatre. Alexandra Smith is a Reader in Russian Studies at the University of Edinburgh and is the author of The Song of the Mockingbird: Pushkin in the Works of Marina Tsvetaeva (1994) and Montaging Pushkin: Pushkin and Visions of Modernity in Russian Twentieth-Century Poetry (2006), as well as numerous articles on Russian literature and culture.</p

    Spatial patterns of mercury risk to piscivorous wading birds of the south central United States

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    Mercury (Hg) is a toxic heavy metal that can pose a risk to birds. Piscivorous birds are exposed to Hg by consuming Hg-contaminated fish. Although there is data on concentrations of Hg in fish, the data on concentrations of Hg in birds is limited. I used a published relationship between concentrations of Hg in the blood of piscivorous birds and concentrations of Hg in prey fish to estimate concentrations of Hg in the blood of four species of piscivorous wading birds in the south central United States. Estimated concentrations of Hg in birds increased with the size of prey fish and increased with conifer-adjusted Hg deposition. This study shows that wading bird species that consume small prey fish are at little risk from exposure to Hg in while those that consume large prey fish are at moderate risk from Hg exposure in ecoregions with high conifer-adjusted Hg deposition

    Normalcy, Knowledge, and Nature in Mark Haddon's The Curious Incident of the Dog in the Night-Time

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    This article analyzes Mark Haddon’s 2003 novel, The Curious Incident of the Dog in the Night-Time, using a combination of both disability studies theory and ecocriticism.  The author argues that the novel’s main character, Christopher Boone, presents a social model of disability by challenging dominant society’s treatment of him as “not normal.” Christopher is ostensibly diagnosed with Asperger’s Syndrome, although the novel never explicitly labels him as disabled in any way. Through Christopher’s views of nature, language, knowledge, and social constructions of disability, we learn that disability is an unstable category, and that dominant society can be disabling.  Importantly, though, Christopher’s critique of society is, as the author argues, fundamentally environmental. That is, Christopher’s views of language, knowledge, and even the more-than-human world itself are central to his destabilization of the category of disability. Christopher’s environmental sensibility and critique of society’s disabling qualities emerge primarily through his discussions of language, which he finds suspect because it distances humans from the world it describes.  Thus, the novel suggests that the disabling features of society that Christopher encounters are the same features that distance humans from nature, particularly through language.  Keywords: eco-phenomenology, ecocriticism, The Curious Incident of the Dog in the Night-Time, Asperger’s Syndrome, nature, language, body, epistemolog

    X-ray characterization of oriented β-tantalum films

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    Tantalum (Ta) metal films (10-70 nm) were deposited on a Si(100) substrate with a 500 nm silicon dioxide (SiO2) interlayer by ion-beam assisted sputtering. The as-deposited films have been characterized by X-ray diffraction (XRD) and X-ray reflectivity (XRR) techniques. XRD measurements showed the presence of films of the tetragonal phase of tantalum (β-Ta) oriented along the (00l) plane. XRR measurements indicated the presence of graded Ta films, with a thin interface layer between the 500 nm SiO2 layer and the Ta films. The thickness and density of this interface layer was estimated to be 1.9±0.2 nm and 10.5±0.5 g/cm3, respectively. X-ray photoelectron spectroscopy (XPS) was used to probe the chemical composition of this interface layer. XPS investigative studies indicated that the interface was likely composed of tantalum silicide (TaSi2) and tantalum silicate (TaSiOx). However, the TaSiOx layer was reduced during Ar ion sputter depth profile analysis

    Radio sources in the Chandra Galactic Bulge Survey

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    We discuss radio sources in the Chandra Galactic Bulge Survey region. By cross-matching the X-ray sources in this field with the NRAO VLA Sky Survey archival data, we find 12 candidate matches. We present a classification scheme for radio/X-ray matches in surveys taken in or near the Galactic plane, taking into account other multiwavelength data. We show that none of the matches found here is likely to be due to coronal activity from normal stars because the radio to X-ray flux ratios are systematically too high. We show that one of the source could be a radio pulsar, and that one could be a planetary nebula, but that the bulk of the sources are likely to be background active galactic nuclei (AGN), with many confirmed through a variety of approaches. Several of the AGN are bright enough in the near-infrared (and presumably in the optical) to use as probes of the interstellar medium in the inner Galaxy

    Structural enzymology using X-ray free electron lasers

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    abstract: Mix-and-inject serial crystallography (MISC) is a technique designed to image enzyme catalyzed reactions in which small protein crystals are mixed with a substrate just prior to being probed by an X-ray pulse. This approach offers several advantages over flow cell studies. It provides (i) room temperature structures at near atomic resolution, (ii) time resolution ranging from microseconds to seconds, and (iii) convenient reaction initiation. It outruns radiation damage by using femtosecond X-ray pulses allowing damage and chemistry to be separated. Here, we demonstrate that MISC is feasible at an X-ray free electron laser by studying the reaction of M. tuberculosis ß-lactamase microcrystals with ceftriaxone antibiotic solution. Electron density maps of the apo-ß-lactamase and of the ceftriaxone bound form were obtained at 2.8 Å and 2.4 Å resolution, respectively. These results pave the way to study cyclic and non-cyclic reactions and represent a new field of time-resolved structural dynamics for numerous substrate-triggered biological reactions

    Lithostratigraphy and clay mineralogy of Paleocene-Eocene thermal maximum sediments at Wilson Lake, NJ

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    The Marlboro Formation is an almost exclusively fine-grained and highly kaolinitic unit deposited during the Paleocene-Eocene Thermal Maximum (ca. 56 Ma). It presents a unique opportunity to study an exceptionally thick carbon isotope excursion and continental shelf sedimentation during a geologically brief episode of global warming. Moreover, the dominantly clayey-silt lithology is traceable over hundreds of kilometers within the Mid-Atlantic Coastal Plain physiographic province and has been drilled at numerous locations. Here, I report lithologic changes within the Marlboro Formation from a corehole at Wilson Lake, NJ to ascertain the environment of deposition and its implications for the isotopic record. Using differences in bedding character, quantified clay mineral identification, fine and coarse fraction grain size analysis, and core scanning x-ray fluorescence of major elements, I show that subtle facies changes are consistent with a shoaling depocenter that is aggrading above a modern shelf clinoform rollover. Previous work has identified the continental shelf adjacent to the Amazon River as a possible analog for the sedimentary environment of the Marlboro Formation. Sedimentary processes and the morphology of the Amazon shelf may be similar to those that produced the Marlboro Formation. Enhanced physical weathering and continental runoff are inferred from the clay mineralogic changes in the PETM section, and are consistent with the PETM climate. Furthermore, the Amazon experiences high rates of deposition in excess of those hypothesized for the New Jersey shelf. Particular clay minerals are also used to demonstrate increased sedimentation rates by measuring the extent of alteration caused by seawater. Rhythmic beds that have previously been interpreted as annual layers based on the periodic cycles in stable isotopes are here interpreted as sediment gravity flow deposits caused by wave-enhanced mud suspensions (fluid mud) like those documented on mud-rich shelves worldwide. The depositional model put forward here supports the extremely rapid onset to the carbon isotope excursion that has been proposed in the shallow marine environment.M.S.Includes bibliographical referencesby Christopher J. Lombard

    Erratum to: Epidermal Growth Factor Receptor (EGFR) Pathway Biomarkers in the Randomized Phase III Trial of Erlotinib Versus Observation in Ovarian Cancer Patients with No Evidence of Disease Progression after First-Line Platinum-Based Chemotherapy (Targ Oncol, 10, 2015 (583-596), 10.1007/s11523-015-0369-6)

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    The original version of this article omitted John A. Green and Christopher Steer from the list of authors. The updated list of author names, their affiliations and an updated conflict of interest statement are shown here. Conflict of Interest Marileila Varella-Garcia is co-inventor on a patent held by the University of Colorado to use EGFR copy number as biomarker for selection of lung cancer patients for targeted therapy. John A. Green received funding for the sample collection and coordination of the samples in the UK (NCRI) from Cancer Research UK. Evelyn Despierre, Ignace Vergote, Ryan Anderson, Corneel Coens, Dionyssios Katsaros, Fred R. Hirsch, Bram Boeckx, Annamaria Ferrero, Isabelle Ray-Coquard, Christopher Steer, Els MJJ Berns, Antonio Casado, Diether Lambrechts, and Antonio Jimeno declare no conflict of interest

    Trade Policy at the Cross-Roads

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    It is now widely agreed that the World Trade Organization (WTO) is in trouble, struggling to deliver the national rewards available from liberalising through multilateral negotiations. Prime Minister Howard and President Bush have committed to help restore the ability of the WTO system to deliver those rewards. This paper examines the contribution of domestic transparency procedures, introduced by and operating within participating countries, in dealing with the domestic causes of the problem facing the multilateral system. It explains the relevance of the proposal, prepared for Prime Minister Howard, in meeting the commitment he has taken. The Hong Kong Ministerial Meeting in December 2005 provides an opportunity to advance such a proposal and, in doing so, enhance our own trade performance. The author was involved, with Alf Rattigan and John Crawford, in establishing the Industries Assistance Commission and was its chairman from 1985 to 1988. He was a member of the international study group chaired by the former Director-General of the GATT, Olivier Long which drew attention during the Uruguay Round of multilateral trade negotiations (1986 1994) to the need for domestic transparency in trade policy. He co-authored a review of trade policy conduct of industrial nations, which was published by the National Centre for Development Studies in 1996. He and Professor Ross Garnaut prepared a domestic transparency proposal for Prime Minister Howard in February 2004 to provide the basis for an Australian initiative in the Doha Round. This paper explains how this proposal would contribute to restoring an effective WTO system by enabling domestic economic welfare to replace domestic political pressures as the driver of multilateral trade negotiations.World Trade Organization, trade, policy, multilateral, negotiations, Howard, Bush
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