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Information about the strength of donor-acceptor interactions in push-pull alkenes is valuable, as this so-called "push-pull effect' influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the CQC double bond to quantify the push-pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in C-13 NMR chemical shifts of the two carbons constituting the CQC double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor-acceptor interactions in the push-pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters ( apparent activation energy Ea and frequency factor A) and activation parameters ( Delta S-double dagger, Delta H-double dagger and Delta G(double dagger)), were determined from the data of the experimentally studied configurational isomerization of ( E)-9a. These results were compared to previously published related data for other two compounds, ( Z)-1b and ( 2E, 5Z)-7, showing that experimentally determined Delta G(double dagger) values are a good indicator of the strength of push-pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated CQC bond lengths and corroborate the applicability of Delta G(double dagger) for estimation of the strength of the push-pull effect in these and related systems.
In June 2013, widespread flooding and consequent damage and losses occurred in Central Europe, especially in Germany. This paper explores what data are available to investigate the adverse impacts of the event, what kind of information can be retrieved from these data and how well data and information fulfil requirements that were recently proposed for disaster reporting on the European and international levels. In accordance with the European Floods Directive (2007/60/EC), impacts on human health, economic activities (and assets), cultural heritage and the environment are described on the national and sub-national scale. Information from governmental reports is complemented by communications on traffic disruptions and surveys of flood-affected residents and companies.
Overall, the impacts of the flood event in 2013 were manifold. The study reveals that flood-affected residents suffered from a large range of impacts, among which mental health and supply problems were perceived more seriously than financial losses. The most frequent damage type among affected companies was business interruption. This demonstrates that the current scientific focus on direct (financial) damage is insufficient to describe the overall impacts and severity of flood events.
The case further demonstrates that procedures and standards for impact data collection in Germany are widely missing. Present impact data in Germany are fragmentary, heterogeneous, incomplete and difficult to access. In order to fulfil, for example, the monitoring and reporting requirements of the Sendai Framework for Disaster Risk Reduction 2015-2030 that was adopted in March 2015 in Sendai, Japan, more efforts on impact data collection are needed.
Climate science today makes use of a variety of red globes to explore and communicate findings. These transform the iconography which informs this image: the idealised, even mythical vision of the blue, vulnerable and perfect marble is impaired by the application of the colours yellow and red. Since only predictions that employ a lot of red seem to exist, spectators are confronted with the message that the future Earth that might turn out as envisaged here is undesirable. Here intuitively powerful narrations of the end of the world may connect. By employing methods of art history and visual analysis, and building on examples from current Intergovernmental Panel on Climate Change reports and future scenario maps, this article explores how burning world images bear - intentionally or not - elements of horror and shock. My question explored here is as follows: should 'burning world' images be understood as a new and powerful cosmology?
The Paleocene was a time of transition for the Arctic, with magmatic activity of the High Arctic Large Igneous Province (HALIP) giving way to magmatism of the North Atlantic Large Igneous Province in connection to plate tectonic changes in the Arctic and North Atlantic. In this study we investigate the Paleocene magmatic record and sediment pathways of the Basilika Formation exposed in the Central Tertiary Basin of Svalbard. By means of geochemistry, SmNd isotopic signatures, and zircon UPb geochronology we investigate the characteristics of several bentonite layers contained in the Basilika Formation, as well as the provenance of the intercalated clastic sediments. Our data show that the volcanic ash layers of the Basilika Formation, which were diagenetically altered to bentonites, originate from alkaline continental-rift magmatism such as the last, explosive stages of the HALIP in North Greenland and the Canadian Arctic. The volcanic ash layers were deposited on Svalbard in a flat shelf environment with dominant sediment supply from the east. Dating of detrital zircons suggests that the detritus was derived from Siberian sources, primarily from the Verkhoyansk Fold-and-Thrust Belt, which would require transport over similar to 3000 km across the Arctic.
Low Earth orbiting geomagnetic satellite missions, such as the Swarm satellite mission, are the only means to monitor and investigate ionospheric currents on a global scale and to make in situ measurements of F region currents. High-precision geomagnetic satellite missions are also able to detect ionospheric currents during quiet-time geomagnetic conditions that only have few nanotesla amplitudes in the magnetic field. An efficient method to isolate the ionospheric signals from satellite magnetic field measurements has been the use of residuals between the observations and predictions from empirical geomagnetic models for other geomagnetic sources, such as the core and lithospheric field or signals from the quiet-time magnetospheric currents. This study aims at highlighting the importance of high-resolution magnetic field models that are able to predict the lithospheric field and that consider the quiet-time magnetosphere for reliably isolating signatures from ionospheric currents during geomagnetically quiet times. The effects on the detection of ionospheric currents arising from neglecting the lithospheric and magnetospheric sources are discussed on the example of four Swarm orbits during very quiet times. The respective orbits show a broad range of typical scenarios, such as strong and weak ionospheric signal (during day- and nighttime, respectively) superimposed over strong and weak lithospheric signals. If predictions from the lithosphere or magnetosphere are not properly considered, the amplitude of the ionospheric currents, such as the midlatitude Sq currents or the equatorial electrojet (EEJ), is modulated by 10-15 % in the examples shown. An analysis from several orbits above the African sector, where the lithospheric field is significant, showed that the peak value of the signatures of the EEJ is in error by 5 % in average when lithospheric contributions are not considered, which is in the range of uncertainties of present empirical models of the EEJ.
Encapsulation of diagnostic and therapeutic compounds in transporters improves their delivery to the point of need. An even more efficient treatment of diseases can be achieved using carriers with targeting or protecting moieties. In the present work, we investigated micellar and liposomal nanocarriers modified with fluorescein, peptides, and polymers that are covalently bound to fatty acids or phospholipids to ensure a self-driven incorporation into the micelles or liposomes. First, we characterized the photophysics of the fluorescent probes in the absence and in the presence of nanocarriers. Changes in the fluorescence decay time, quantum yield, and intensity of a fluorescein-labeled fatty acid (fluorescein-labeled palmitic acid [fPA]) and a fluorescein-labeled lipopeptide (P2fA2) were found. By exploiting these changes, we investigated a lipopeptide (P2A2 as an uptake-mediating unit) in combination with different nanocarriers (micelles and liposomes) and determined the corresponding association constant K-ass values, which were found to be very high. In addition, the mobility of fPA was exploited using fluorescence correlation spectroscopy (FCS) and fluorescence depolarization (FD) experiments to characterize the nanocarriers. Cellular uptake experiments with mouse brain endothelial cells provided information on the uptake behavior of liposomes modified by uptake-mediating P2A2 and revealed differences in the uptake behavior between pH-sensitive and pH-insensitive liposomes.
We study the modeling and prediction of dynamical systems based on conventional models derived from measurements. Such algorithms are highly desirable in situations where the underlying dynamics are hard to model from physical principles or simplified models need to be found. We focus on symbolic regression methods as a part of machine learning. These algorithms are capable of learning an analytically tractable model from data, a highly valuable property. Symbolic regression methods can be considered as generalized regression methods. We investigate two particular algorithms, the so-called fast function extraction which is a generalized linear regression algorithm, and genetic programming which is a very general method. Both are able to combine functions in a certain way such that a good model for the prediction of the temporal evolution of a dynamical system can be identified. We illustrate the algorithms by finding a prediction for the evolution of a harmonic oscillator based on measurements, by detecting an arriving front in an excitable system, and as a real-world application, the prediction of solar power production based on energy production observations at a given site together with the weather forecast.
Antibodies against spike proteins of influenza are used as a tool for characterization of viruses and therapeutic approaches. However, development, production and quality control of antibodies is expensive and time consuming. To circumvent these difficulties, three peptides were derived from complementarity determining regions of an antibody heavy chain against influenza A spike glycoprotein. Their binding properties were studied experimentally, and by molecular dynamics simulations. Two peptide candidates showed binding to influenza A/Aichi/2/68 H3N2. One of them, termed PeB, with the highest affinity prevented binding to and infection of target cells in the micromolar region without any cytotoxic effect. PeB matches best the conserved receptor binding site of hemagglutinin. PeB bound also to other medical relevant influenza strains, such as human-pathogenic A/California/7/2009 H1N1, and avian-pathogenic A/MuteSwan/Rostock/R901/2006 H7N1. Strategies to improve the affinity and to adapt specificity are discussed and exemplified by a double amino acid substituted peptide, obtained by substitutional analysis. The peptides and their derivatives are of great potential for drug development as well as biosensing.
Earthworms play a key role in regulating soil ecosystem functions and services. The small scale variability in earthworm abundance is often found to be very high, which is a problem for representative sampling of earthworm abundance at larger scales. In agricultural fields, soil tillage may influence both the average earthworm abundance as well as the spatial distribution of earthworms. Therefore we studied the abundance and spatial pattern of the different ecological earthworm types, i.e. endogeic, epigeic and anecic earthworms, in four agricultural fields differing in soil tillage (two fields with regular tillage and two fields with conservation tillage) and surrounding land use (other cropped fields or apple orchard and forest). To this aim we sampled earthworms on a total number of 430 plots (50 x 50 cm(2)) using a combination of extraction with mustard solution and hand sorting. The results exhibit large differences in average earthworm abundance between the four fields. Only one of the two fields with conservation tillage had a comparatively very high overall abundance of earthworms. Furthermore, we found a high spatial variability of earthworms within the field scale often exhibiting a patchy distribution. We detected a trend of decreasing earthworm abundances from the field border into the field for different earthworm groups on each of the fields. In three fields with low total earthworm abundance (and only very few epigeic earthworms) there was a short scale autocorrelation with ranges varying strongly for the endogeic earthworms (37.9 m, 62.6 m, and 85.2 m) compared to anecic earthworms (19.8 m, 22.8 m, and 27.4 m). In the field with high abundance, after trend removal, the variogram models for anecic and endogeic earthworms were rejected based on their negative explained variances. On this field, we found only a short scale autocorrelation for the epigeic earthworms with a range of 143 m. Based on these results it seems that ploughing alone cannot explain the differences in abundance and range of autocorrelation found on the four fields. The trend of strongly decreasing earthworm abundance from the field border into the field in the one field with high abundance does indicate that the field border or surrounding land use may also influence the recolonization of fields, but more research is required to provide further evidence for this hypothesis. Due to the very different patterns of earthworm distributions in the fields it remains difficult to recommend an optimal number and distance of samples to obtain a representative earthworm abundance for the field scale. (C) 2016 Elsevier B.V. All rights reserved.
In this study, we investigated the scale sizes of equatorial plasma irregularities (EPIs) using measurements from the Swarm satellites during its early mission and final constellation phases. We found that with longitudinal separation between Swarm satellites larger than 0.4 degrees, no significant correlation was found any more. This result suggests that EPI structures include plasma density scale sizes less than 44 km in the zonal direction. During the Swarm earlier mission phase, clearly better EPI correlations are obtained in the northern hemisphere, implying more fragmented irregularities in the southern hemisphere where the ambient magnetic field is low. The previously reported inverted-C shell structure of EPIs is generally confirmed by the Swarm observations in the northern hemisphere, but with various tilt angles. From the Swarm spacecrafts with zonal separations of about 150 km, we conclude that larger zonal scale sizes of irregularities exist during the early evening hours (around 1900 LT).