187 research outputs found

    A selected ion flow tube study of the ion-molecule reactions of monochloroethene, trichloroethene and tetrachloroethene

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    Data for the rate coefficients and product cations of the reactions of a large number of atomic and small molecular cations with monochloroethene, trichloroethene and tetrachloroethene in a selected ion flow tube at 298 K are reported. The recombination energy of the ions range from 6.27 eV (H3_3O+^+) through to 21.56 eV (Ne+^+). Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental values. Thermochemistry and mass balance predict the most feasible neutral products. Together with previously reported results for the three isomers of dichloroethene (J. Phys. Chem. A., 2006, 110, 5760), the fragment ion branching ratios have been compared with those from threshold photoelectron photoion coincidence spectroscopy over the photon energy range 9-22 eV to determine the importance or otherwise of long-range charge transfer. For ions with recombination energy in excess of the ionisation energy of the chloroethene, charge transfer is energetically allowed. The similarity of the branching ratios from the two experiments suggest that long-range charge transfer is dominant. For ions with recombination energy less than the ionisation energy, charge transfer is not allowed; chemical reaction can only occur following formation of an ion-molecule complex, where steric effects are more significant. The products that are now formed and their percentage yield is a complex interplay between the number and position of the chlorine atoms with respect to the C=C bond, where inductive and conjugation effects can be important

    Long-Billed Curlew Nest Site Selection and Success in the Intermountain West

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    Grassland birds have experienced steeper population declines between 1966 and 2015 than any other bird group on the North American continent, and migratory grassland birds may face threats in all stages of their annual cycle. The grassland‐associated long‐billed curlew (Numenius americanus) is experiencing population declines in regional and local portions of their North American breeding range. The nesting period is an important portion of the annual cycle when curlews may face demographic rate limitations from a suite of threats including predators and anthropogenic disturbance. We compared nest sites to random sites within breeding territories to examine nest site selection, and modeled correlates of nesting success for 128 curlew nests at 5 Intermountain West sites. Nest sites were 6 times more likely than random sites to be situated adjacent to existing cowpies. Additionally, curlews selected nest sites with shorter vegetation, and less bare ground, grass, and shrub cover than at random sites within their territories. Nest success varied widely among sites and ranged from 12% to 40% in a season with a mean of 27% for all nests during the 2015 and 2016 seasons. Higher nest success probability was associated with higher curlew densities in the area, greater percent cover of conspicuous objects (cowpies, rocks) near the nest, and higher densities of black‐billed magpies (Pica hudsonia) and American crows (Corvus brachyrhynchos) at the site. We also found increased probability of nesting success with increased distance from a nest to the nearest potential perch in that territory. Given the central role of working lands to curlews in much of the Intermountain West, understanding limitations to nesting success in these diverse landscapes is necessary to guide adaptive management strategies in increasingly human‐modified habitats. We suggest some grazing and irrigation practices already provide suitable nesting conditions for curlews, and others may require only minor temporal shifts to improve compatibility

    Preparation of amino-substituted indenes and 1,4-dihydronaphthalenes using a one-pot multireaction approach: total synthesis of oxybenzo[c]phenanthridine alkaloids

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    Allylic trichloroacetimidates bearing a 2-vinyl or 2-allylaryl group have been designed as substrates for a one-pot, two-step multi-bond-forming process leading to the general preparation of aminoindenes and amino-substituted 1,4-dihydronaphthalenes. The synthetic utility of the privileged structures formed from this one-pot process was demonstrated with the total synthesis of four oxybenzo[c]phenanthridine alkaloids, oxychelerythrine, oxysanguinarine, oxynitidine, and oxyavicine. An intramolecular biaryl Heck coupling reaction, catalyzed using the Hermann–Beller palladacycle was used to effect the key step during the synthesis of the natural products

    Phenotypic spectrum and transcriptomic profile associated with germline variants in TRAF7

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    PURPOSE: Somatic variants in tumor necrosis factor receptor-associated factor 7 (TRAF7) cause meningioma, while germline variants have recently been identified in seven patients with developmental delay and cardiac, facial, and digital anomalies. We aimed to define the clinical and mutational spectrum associated with TRAF7 germline variants in a large series of patients, and to determine the molecular effects of the variants through transcriptomic analysis of patient fibroblasts. METHODS: We performed exome, targeted capture, and Sanger sequencing of patients with undiagnosed developmental disorders, in multiple independent diagnostic or research centers. Phenotypic and mutational comparisons were facilitated through data exchange platforms. Whole-transcriptome sequencing was performed on RNA from patient- and control-derived fibroblasts. RESULTS: We identified heterozygous missense variants in TRAF7 as the cause of a developmental delay-malformation syndrome in 45 patients. Major features include a recognizable facial gestalt (characterized in particular by blepharophimosis), short neck, pectus carinatum, digital deviations, and patent ductus arteriosus. Almost all variants occur in the WD40 repeats and most are recurrent. Several differentially expressed genes were identified in patient fibroblasts. CONCLUSION: We provide the first large-scale analysis of the clinical and mutational spectrum associated with the TRAF7 developmental syndrome, and we shed light on its molecular etiology through transcriptome studies

    Установление границ охранной зоны линейного сооружения – магистральный газопровод "НГПЗ - Парабель"

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    Составлено графическое описание местоположения границ зон с особыми условиями использования территорий границ охранной зоны линейного сооружения – магистральный газопровод "НГПЗ - Парабель".A graphic description of the location of the boundaries of the zones with special conditions for the use of the territories of the boundaries of the protection zone of the linear structure – "the NGPZ-Parabel" gas pipeline has been compiled

    Atmos. Environ.

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    CO concentration and its isotopic composition (C-13, C-14, O-17 and O-18) are used to characterize air pollution events observed at Schauinland, Germany. in August 2000. After determination of the background signal, we could identify and characterize five pollution events. Particularly, (CO)-C-14 and delta(18)O variations help to determine the nature of the pollution source (fossil fuel or biomass combustion) and its origin (local or regional/continental). By using a box model, further information about the age of the polluted air mass is derived. We particularly establish that one polluted air mass was about 10 days old and that this event was due to long-range transport of products emitted from forest fires in Canada. (C) 2002 Elsevier Science Ltd. All rights reserved
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