25 research outputs found

    Anionic N-heterocyclic carbenes by decarboxylation of sydnone-4-carboxylates

    Get PDF
    Unstable N-heterocyclic carbenes can be masked and stabilized as pseudo-cross-conjugated hetarenium-carboxylates which decarboxylate on warming. This study deals with the decarboxylation of carboxylates of mesoionic compounds to generate anionic N-heterocyclic carbenes. Lithium sydnone-4-carboxylates were therefore prepared via 4-bromosydnones by halogen-lithium exchange with nBuLi and subsequent treatment with carbon dioxide. Protonation gave the corresponding sydnone-4-carboxylic acids. Thermogravimetric measurements in addition to temperature dependent IR spectroscopy proved the decarboxylation of lithium sydnone-4-carboxylates and formation of the corresponding sydnone anions which can be represented as anionic N-heterocyclic carbenes. In DMSO-d6 solution, water favors the decarboxylation. Calculations have been performed to elucidate the mechanism of the decarboxylation in the absence and presence of water. (C) 2018 Elsevier Ltd. All rights reserved.Peer reviewe

    Impacts of forest conversion and agriculture practices on water pathways in Southern Brazil

    No full text
    © 2018 John Wiley & Sons, Ltd. Land-use/cover change (LUCC), and more specifically deforestation and multidecadal agriculture, is one of the various controlling factors of water fluxes at the hillslope or catchment scale. We investigated the impact of LUCC on water pathways and stream stormflow generation processes in a subtropical region in southern Brazil. We monitored, sampled and analysed stream water, pore water, subsurface water, and rainwater for dissolved silicon concentration (DSi) and 18O/16O (δ18O) signature to identify contributing sources to the streamflow under forest and under agriculture. Both forested and agricultural catchments were highly responsive to rainfall events in terms of discharge and shallow groundwater level. DSi versus δ18O scatter plots indicated that for both land-use types, two run-off components contributed to the stream discharge. The presence of a dense macropore network, combined with the presence of a compact and impeding B-horizon, led to rapid subsurface flow in the forested catchment. In the agricultural catchment, the rapid response to rainfall was mostly due to surface run-off. A 2-component isotopic hydrograph separation indicated a larger contribution of rainfall water to run-off during rainfall event in the agricultural catchments. We attributed this higher contribution to a decrease in topsoil hydraulic conductivity associated with agricultural practices. The chemical signature of the old water component in the forested catchment was very similar to that of the shallow groundwater and the pore soil water: It is therefore likely that the shallow groundwater was the main source of old water. This is not the case in the agricultural catchments where the old water component had a much higher DSi concentration than the shallow groundwater and the soil pore water. As the agricultural catchments were larger, this may to some extent simply be a scale effect. However, the higher water yields under agriculture and the high DSi concentration observed in the old water under agriculture suggest a significant contribution of deep groundwater to catchment run-off under agriculture, suggesting that LUCC may have significant effects on weathering rates and patterns.status: publishe

    Potential Applications of Flat-Panel Volumetric CT in Morphologic and Functional Small Animal Imaging

    Get PDF
    Noninvasive radiologic imaging has recently gained considerable interest in basic and preclinical research for monitoring disease progression and therapeutic efficacy. In this report, we introduce flat-panel volumetric computed tomography (fpVCT) as a powerful new tool for noninvasive imaging of different organ systems in preclinical research. The three-dimensional visualization that is achieved by isotropic high-resolution datasets is illustrated for the skeleton, chest, abdominal organs, and brain of mice. The high image quality of chest scans enables the visualization of small lung nodules in an orthotopic lung cancer model and the reliable imaging of therapy side effects such as lung fibrosis. Using contrast-enhanced scans, fpVCT displayed the vascular trees of the brain, liver, and kidney down to the subsegmental level. Functional application of fpVCT in dynamic contrast-enhanced scans of the rat brain delivered physiologically reliable data of perfusion and tissue blood volume. Beyond scanning of small animal models as demonstrated here, fpVCT provides the ability to image animals up to the size of primates
    corecore