2,785 research outputs found

    An equivalent layer magnetization model for the United States derived from MAGSAT data

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    Long wavelength anomalies in the total magnetic field measured field measured by MAGSAT over the United States and adjacent areas are inverted to an equivalent layer crustal magnetization distribution. The model is based on an equal area dipole grid at the Earth's surface. Model resolution having physical significance, is about 220 km for MAGSAT data in the elevation range 300-500 km. The magnetization contours correlate well with large-scale tectonic provinces

    Isomeric effects in the gas-phase reactions of dichloroethene, C2H2Cl2, with a series of cations

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    A study of the reactions of a series of gas-phase cations (NH4+_4^+, H3_3O+^+, SF3+_3^+, CF3+_3^+, CF+^+, SF5+^+, SF2+_2^+, SF+^+, CF2+_2^+, SF4+_4^+, O2+_2^+, Xe+^+, N2_2O+^+, CO2+_2^+, Kr+^+, CO+^+, N+^+, N2+_2^+, Ar+^+, F+^+ and Ne+^+) with the three structural isomers of dichloroethene, i.e. 1,1-C2_2H2_2Cl2_2, cis-1,2-C2_2H2_2Cl2_2 and trans-1,2-C2_2H2_2Cl2_2 is reported. The recombination energy of these ions spans the range 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube. Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C2_2H2_2Cl2_2 with photon energies in the range 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H3_3O+^+, CF3+_3^+, and CF+^+. For 1,1-C2_2H2_2Cl2_2 the reaction with H3_3O+^+ proceeds at the collisional rate with the only ionic product being 1,1-C2_2H2_2Cl2_2H+^+. However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C2_2H2_2Cl2_2, but only proceeds with 14 % and 18 % efficiency, respectively. The CF3+_3^+ reaction proceeds with 56-80 % efficiency, the only ionic product for 1,1-C2_2H2_2Cl2_2 being C2_2H2_2Cl+^+ formed via Cl- abstraction, whereas the only ionic product for both 1,2-isomers is CHCl2+_2^+ corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C2_2H2_2Cl2_2 isomers, have been found in the reactions of SF+^+, CO2+_2^+, CO+^+, N2+_2^+, and Ar+^+. Although these five ions have recombination energies above the ionization energy of any of the C2_2H2_2Cl2_2 isomers and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C2_2H2_2Cl2_2 is responsible for the observed effects

    A Selected Ion Flow Tube Study of the Reactions of Several Cations with the Group 6B Hexafluorides SF6, SeF6, and TeF6

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    The first investigation of the ion chemistry of SeF6_6 and TeF6_6 is presented. Using a selected ion flow tube, the thermal rate coefficients and ion product distributions have been determined at 300 K for the reactions of fourteen atomic and molecular cations, namely H3_3O+^+, CF3+_3^+, CF+^+, CF2+_2^+, H2_2O+^+, N2_2O+^+, O+^+, CO2+_2^+, CO+^+, N+^+, N2+_2^+, Ar+^+, F+^+ and Ne+^+ (in order of increasing recombination energy), with SeF6_6 and TeF6_6. The results are compared with those from the reactions of these ions with SF6_6, for which the reactions with CF+^+, CF2+_2^+, N2_2O+^+ and F+^+ are reported for the first time. Several distinct processes are observed amongst the large number of reactions studied, including dissociative charge transfer, and F^-, F, F2_2^- and F2_2 abstraction from the neutral reactant molecule to the reagent ion. The dissociative charge transfer channels are discussed in relation to vacuum ultraviolet photoelectron and threshold photoelectron-photoion coincidence spectra of XF6_6 (X = S, Se, and Te). For reagent ions whose recombination energies lie between the first dissociative ionisation limit, XF6_6 \rightarrow XF5+_5^+ + F + e^-, and the onset of ionisation of the XF6_6 molecule, the results suggest that if dissociative charge transfer occurs, it proceeds via an intimate encounter. For those reagent ions whose recombination energies are greater than the onset of ionisation, long-range electron transfer may occur depending on whether certain physical factors apply, for example non-zero Franck-Condon overlap. From the reaction kinetics, limits for the heats of formation of SeF4_4, SeF5_5, TeF4_4 and TeF5_5 at 298 K have been obtained; Δf\Delta_fHo^o(SeF4_4) < -369 kJ mol1^{-1}, Δf\Delta_fHo^o(SeF5_5) < -621 kJ mol1^{-1}, Δf\Delta_fHo^o(TeF4_4) > -570 kJ mol1^{-1}, and Δf\Delta_fHo^o(TeF5_5) < -822 kJ mol1^{-1}

    Threshold photoelectron photoion coincidence spectroscopy and selected ion flow tube reactions of CHF3: comparison of product branching ratios

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    The threshold photoelectron and threshold photoelectron photoion coincidence spectra of CHF3_3 in the range 13.5 – 24.5 eV have been recorded. Ion yields and branching ratios have been determined for the three fragments CF3+_3^+, CHF2+^+ and CF+^+. The mean kinetic energy releases into fragment ions involving either C-H or C-F bond cleavage have been measured, and compared with statistical and impulsive models. CHF3+_3^+ behaves in a non-statistical manner characteristic of the small-molecule limit, with the ground electronic state and low-lying excited states of CHF3+_3^+ being largely repulsive along the C-H and C-F coordinates, respectively. The rate coefficients and product ion branching ratios have been measured at 298 K in a selected ion flow tube for the reactions of CHF3_3 with a large number of gas-phase cations whose recombination energies span the range 6.3 through 21.6 eV. A comparison between the branching ratios from the two experiments, together with an analysis of the threshold photoelectron spectrum of CHF3_3, shows that long-range charge transfer probably occurs for the Ar+^+ and F+^+ atomic ions whose recombination energies lie above ca. 15 eV. Below this energy, the mechanism involves a combination of short-range charge transfer and chemical reactions involving a transition state intermediate

    A study of the gas-phase reactions of various cations with two derivatives of SF6 : SF5CF3 and SF5Cl

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    A selected ion flow tube apparatus was used to investigate the positive ion chemistry of two derivatives of SF6_6; SF5_5CF3_3 and SF5_5Cl. This represents the first investigation of the positive ion chemistry of SF5_5Cl, and much of the data on SF5_5CF3_3 is being presented here for the first time. Rate coefficients and ion product branching ratios have been determined at room temperature (300 K) for reactions with the following twenty-two cations; Ne+^+, F+^+, Ar+^+, N2+_2^+, N+^+, CO+^+, CO2+_2^+, O+^+, N2_2O+^+, H2_2O+^+, O2+_2^+, SF4+^+, CF2+_2^+, SF+^+, SF2+_2^+, NO2+_2^+, SF5+_5^+, NO+^+, CF+^+, CF3+_3^+, SF3+_3^+, and H3_3O+^+ (listed in order of decreasing recombination energy). Comparisons are made in the text for the reactions of these ions with SF6_6. SF2+_2^+, NO2+_2^+, NO+^+, SF3+_3^+, and H3_3O+^+ are found to be unreactive with both of the derivatives. The majority of the other reactions proceed with rate coefficients which are close to the capture value. The exceptions are the reactions of O2+_2^+, SF+^+, SF5+_5^+, and CF3+_3^+ with SF5_5CF3_3, and SF4+^+ and SF5+_5^+ with SF5_5Cl, all of which have rate coefficients significantly less than the capture mechanism value. Several distinct processes are observed among the large number of reactions studied, including dissociative charge transfer and various abstraction channels. Non-dissociative charge transfer is not observed, implying that any parent ions formed dissociate rapidly to the fragment ions and associated neutrals

    The Arabidopsis thaliana mobilome and its impact at the species level

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    Transposable elements (TEs) are powerful motors of genome evolution yet a comprehensive assessment of recent transposition activity at the species level is lacking for most organisms. Here, using genome sequencing data for 211 Arabidopsis thaliana accessions taken from across the globe, we identify thousands of recent transposition events involving half of the 326 TE families annotated in this plant species. We further show that the composition and activity of the 'mobilome' vary extensively between accessions in relation to climate and genetic factors. Moreover, TEs insert equally throughout the genome and are rapidly purged by natural selection from gene-rich regions because they frequently affect genes, in multiple ways. Remarkably, loci controlling adaptive responses to the environment are the most frequent transposition targets observed. These findings demonstrate the pervasive, species-wide impact that a rich mobilome can have and the importance of transposition as a recurrent generator of large-effect alleles

    Flight Lieutenant Peach's observations on Burning Feet Syndrome in Far Eastern Prisoners of War 1942-45.

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    Introduction: ‘Burning Feet Syndrome’ affected up to one third of Far Eastern Prisoners of War in World War 2. Recently discovered medical records, produced by RAF Medical Officer Nowell Peach whilst in captivity, are the first to detail neurological examinations of patients with this condition. Methods: The 54 sets of case notes produced at the time were analysed using modern diagnostic criteria to determine if the syndrome can be retrospectively classed as neuropathic pain. Results: With a history of severe malnutrition raising the possibility of a peripheral polyneuropathy, and a neuroanatomically plausible pain distribution, this analysis showed that Burning Feet Syndrome can now be described as a ‘possible’ neuropathic pain syndrome. Conclusion: After 70 years, the data painstakingly gathered under the worst of circumstances have proved to be of interest and value in modern diagnostics of neuropathic pain

    Epithelial cell shedding and barrier function: a matter of life and death at the small intestinal villus tip

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    The intestinal epithelium is a critical component of the gut barrier. Composed of a single layer of intestinal epithelial cells (IECs) held together by tight junctions, this delicate structure prevents the transfer of harmful microorganisms, antigens, and toxins from the gut lumen into the circulation. The equilibrium between the rate of apoptosis and shedding of senescent epithelial cells at the villus tip, and the generation of new cells in the crypt, is key to maintaining tissue homeostasis. However, in both localized and systemic inflammation, this balance may be disturbed as a result of pathological IEC shedding. Shedding of IECs from the epithelial monolayer may cause transient gaps or microerosions in the epithelial barrier, resulting in increased intestinal permeability. Although pathological IEC shedding has been observed in mouse models of inflammation and human intestinal conditions such as inflammatory bowel disease, understanding of the underlying mechanisms remains limited. This process may also be an important contributor to systemic and intestinal inflammatory diseases and gut barrier dysfunction in domestic animal species. This review aims to summarize current knowledge about intestinal epithelial cell shedding, its significance in gut barrier dysfunction and host-microbial interactions, and where research in this field is directed
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