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The molecular structures of four bis-ligated high-spin Ni(II) complexes of the sterically crowded, nonplanar 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetranitroporphytin (NiOETNP) are reported. The ligands are imidazole (Im), imidazole plus 2-methylimidazole (2-MeIm) in the crystal lattice, 1-methylimidazole (1-MeIm), and 2,1,3- benzoselenadiazole (BSeD). Extensive intermolecular hydrogen bonding is observed in the three imidazole-ligated structures consisting of NH...O and CH...O bonding from the imidazoles to neighboring nitro groups and of NH...N interactions to a nearby 2-MeIm. The different modes of hydrogen bonding, typical of those frequently observed in proteins, mediate the self-assembly of discrete porphyrin dimers as well as more extensive two- and three-dimensional arrays. Only the bis-BSeD complex remains monomeric. The presence or absence of the different types of hydrogen bonds controls the orientations of the axial ligands and also modulates the conformations of the porphyrin skeletons. This interplay of axial ligation, hydrogen bonding, and self-assembly further illustrates the multi conformational landscapes that porphyrins can access as a function of their microenvironment. Such nonplanar deformations have been shown to significantly affect the optical, redox, magnetic, radical, and excited state properties of porphyrin derivatives. That hydrogen bonding can influence ligand interactions with neighboring functional groups as well as macrocycle conformations with their concomitant consequences on physical and chemical properties may thus be particularly relevant to the bioenergetic roles of porphyrin in vivo. These results also raise the question whether point mutations near porphyrins in vivo are structurally, and consequently functionally, innocent
Ground-based gamma-ray astronomy has had a major breakthrough with the impressive results obtained using systems of imaging atmospheric Cherenkov telescopes. Ground-based gamma-ray astronomy has a huge potential in astrophysics, particle physics and cosmology. CTA is an international initiative to build the next generation instrument, with a factor of 5-10 improvement in sensitivity in the 100 GeV-10 TeV range and the extension to energies well below 100 GeV and above 100 TeV. CTA will consist of two arrays (one in the north, one in the south) for full sky coverage and will be operated as open observatory. The design of CTA is based on currently available technology. This document reports on the status and presents the major design concepts of CTA.
Silvicultural practices lead to changes in forest composition and structure and may impact species diversity from the overall regional species pool to stand-level species occurrence. We explored to what extent fine-scale occupancy patterns in differently managed forest stands are driven by environment and ecological traits in three regions in Germany using a multi-species hierarchical model. We tested for the possible impact of environmental variables and ecological traits on occupancy dynamics in a joint modelling exercise while taking possible variation in coefficient estimates over years and plots into account. Bird species richness differed across regions and years, and trends in species richness across years were different in the three regions. On the species level, forest management affected occupancy of species in all regions, but only 35% of the total assemblage-level variation in occurrence probability was explained by either forest type and successional stage and <?1% by forest edge. On the assemblage level, bird occurrence decreased with body mass in all regions. Species with smaller breeding ranges had lower occurrence probabilities in one region, while later spring arrival decreased occurrence probabilities in the two other regions. Spatial variation in the effect size of trait covariates such as species phylogeny and breeding strata showed that variation in patch occupancy due to fine-scale differences in forest management is, to some extent, predictable from ecological traits. Our results show that environmental factors and ecological traits jointly predict variation in bird occupancy patterns and their response to forest management. Observations at the fine scale of forest stands, at which conservation efforts can be arranged along with forest management practices in heterogeneous environments, have been shown to provide meaningful insights despite the difficulties involved in monitoring mobile organisms such as birds at the plot level.
Organic management is one of the most popular strategies to reduce negative environmental impacts of intensive agriculture. However, little is known about benefits for biodiversity and potential worsening of yield under organic grasslands management across different grassland types, i.e. meadow, pasture and mown pasture. Therefore, we studied the diversity of vascular plants and foliage-living arthropods (Coleoptera, Araneae, Heteroptera, Auchenorrhyncha), yield, fodder quality, soil phosphorus concentrations and land-use intensity of organic and conventional grasslands across three study regions in Germany. Furthermore, all variables were related to the time since conversion to organic management in order to assess temporal developments reaching up to 18 years. Arthropod diversity was significantly higher under organic than conventional management, although this was not the case for Araneae, Heteroptera and Auchenorrhyncha when analyzed separately. On the contrary, arthropod abundance, vascular plant diversity and also yield and fodder quality did not considerably differ between organic and conventional grasslands. Analyses did not reveal differences in the effect of organic management among grassland types. None of the recorded abiotic and biotic parameters showed a significant trend with time since transition to organic management, except soil organic phosphorus concentrations which decreased with time. This implies that permanent grasslands respond slower and probably weaker to organic management than crop fields do. However, as land-use intensity and inorganic soil phosphorus concentrations were significantly lower in organic grasslands, overcoming seed and dispersal limitation by re-introducing plant species might be needed to exploit the full ecological potential of organic grassland management. We conclude that although organic management did not automatically increase the diversity of all studied taxa, it is a reasonable and useful way to support agro-biodiversity.
Introducing the CTA concept
(2013)
The Cherenkov Telescope Array (CTA) is a new observatory for very high-energy (VHE) gamma rays. CTA has ambitions science goals, for which it is necessary to achieve full-sky coverage, to improve the sensitivity by about an order of magnitude, to span about four decades of energy, from a few tens of GeV to above 100 TeV with enhanced angular and energy resolutions over existing VHE gamma-ray observatories. An international collaboration has formed with more than 1000 members from 27 countries in Europe, Asia, Africa and North and South America. In 2010 the CTA Consortium completed a Design Study and started a three-year Preparatory Phase which leads to production readiness of CTA in 2014. In this paper we introduce the science goals and the concept of CTA, and provide an overview of the project.
Although temporal heterogeneity is a well-accepted driver of biodiversity, effects of interannual variation in land-use intensity (LUI) have not been addressed yet. Additionally, responses to land use can differ greatly among different organisms; therefore, overall effects of land-use on total local biodiversity are hardly known. To test for effects of LUI (quantified as the combined intensity of fertilization, grazing, and mowing) and interannual variation in LUI (SD in LUI across time), we introduce a unique measure of whole-ecosystem biodiversity, multidiversity. This synthesizes individual diversity measures across up to 49 taxonomic groups of plants, animals, fungi, and bacteria from 150 grasslands. Multidiversity declined with increasing LUI among grasslands, particularly for rarer species and aboveground organisms, whereas common species and belowground groups were less sensitive. However, a high level of interannual variation in LUI increased overall multidiversity at low LUI and was even more beneficial for rarer species because it slowed the rate at which the multidiversity of rare species declined with increasing LUI. In more intensively managed grasslands, the diversity of rarer species was, on average, 18% of the maximum diversity across all grasslands when LUI was static over time but increased to 31% of the maximum when LUI changed maximally over time. In addition to decreasing overall LUI, we suggest varying LUI across years as a complementary strategy to promote biodiversity conservation.
Land-use intensification is a key driver of biodiversity change. However, little is known about how it alters relationships between the diversities of different taxonomic groups, which are often correlated due to shared environmental drivers and trophic interactions. Using data from 150 grassland sites, we examined how land-use intensification (increased fertilization, higher livestock densities, and increased mowing frequency) altered correlations between the species richness of 15 plant, invertebrate, and vertebrate taxa. We found that 54% of pairwise correlations between taxonomic groups were significant and positive among all grasslands, while only one was negative. Higher land-use intensity substantially weakened these correlations(35% decrease in rand 43% fewer significant pairwise correlations at high intensity), a pattern which may emerge as a result of biodiversity declines and the breakdown of specialized relationships in these conditions. Nevertheless, some groups (Coleoptera, Heteroptera, Hymenoptera and Orthoptera) were consistently correlated with multidiversity, an aggregate measure of total biodiversity comprised of the standardized diversities of multiple taxa, at both high and lowland-use intensity. The form of intensification was also important; increased fertilization and mowing frequency typically weakened plant-plant and plant-primary consumer correlations, whereas grazing intensification did not. This may reflect decreased habitat heterogeneity under mowing and fertilization and increased habitat heterogeneity under grazing. While these results urge caution in using certain taxonomic groups to monitor impacts of agricultural management on biodiversity, they also suggest that the diversities of some groups are reasonably robust indicators of total biodiversity across a range of conditions.
The results of streamflow trend studies are often characterized by mostly insignificant trends and inexplicable spatial patterns. In our study region, Western Austria, this applies especially for trends of annually averaged runoff. However, analysing the altitudinal aspect, we found that there is a trend gradient from higher-altitude to lower-altitude stations, i.e. a pattern of mostly positive annual trends at higher stations and negative ones at lower stations. At mid-altitudes, the trends are mostly insignificant. Here we hypothesize that the streamflow trends are caused by the following two main processes: on the one hand, melting glaciers produce excess runoff at higher-altitude watersheds. On the other hand, rising temperatures potentially alter hydrological conditions in terms of less snowfall, higher infiltration, enhanced evapotranspiration, etc., which in turn results in decreasing streamflow trends at lower-altitude watersheds. However, these patterns are masked at mid-altitudes because the resulting positive and negative trends balance each other. To support these hypotheses, we attempted to attribute the detected trends to specific causes. For this purpose, we analysed trends of filtered daily streamflow data, as the causes for these changes might be restricted to a smaller temporal scale than the annual one. This allowed for the explicit determination of the exact days of year (DOYs) when certain streamflow trends emerge, which were then linked with the corresponding DOYs of the trends and characteristic dates of other observed variables, e.g. the average DOY when temperature crosses the freezing point in spring. Based on these analyses, an empirical statistical model was derived that was able to simulate daily streamflow trends sufficiently well. Analyses of subdaily streamflow changes provided additional insights. Finally, the present study supports many modelling approaches in the literature which found out that the main drivers of alpine streamflow changes are increased glacial melt, earlier snowmelt and lower snow accumulation in wintertime.
The results of streamflow trend studies are often characterized by mostly insignificant trends and inexplicable spatial patterns. In our study region, Western Austria, this applies especially for trends of annually averaged runoff. However, analysing the altitudinal aspect, we found that there is a trend gradient from higher-altitude to lower-altitude stations, i.e. a pattern of mostly positive annual trends at higher stations and negative ones at lower stations. At midaltitudes, the trends are mostly insignificant. Here we hypothesize that the streamflow trends are caused by the following two main processes: on the one hand, melting glaciers produce excess runoff at higher-altitude watersheds. On the other hand, rising temperatures potentially alter hydrological conditions in terms of less snowfall, higher infiltration, enhanced evapotranspiration, etc., which in turn results in decreasing streamflow trends at lower-altitude watersheds. However, these patterns are masked at mid-altitudes because the resulting positive and negative trends balance each other. To support these hypotheses, we attempted to attribute the detected trends to specific causes. For this purpose, we analysed trends of filtered daily streamflow data, as the causes for these changes might be restricted to a smaller temporal scale than the annual one. This allowed for the explicit determination of the exact days of year (DOYs) when certain streamflow trends emerge, which were then linked with the corresponding DOYs of the trends and characteristic dates of other observed variables, e.g. the average DOY when temperature crosses the freezing point in spring. Based on these analyses, an empirical statistical model was derived that was able to simulate daily streamflow trends sufficiently well. Analyses of subdaily streamflow changes provided additional insights. Finally, the present study supports many modelling approaches in the literature which found out that the main drivers of alpine streamflow changes are increased glacial melt, earlier snowmelt and lower snow accumulation in wintertime.
The results of streamflow trend studies are often characterized by mostly insignificant trends and inexplicable spatial patterns. In our study region, Western Austria, this applies especially for trends of annually averaged runoff. However, analysing the altitudinal aspect, we found that there is a trend gradient from higher-altitude to lower-altitude stations, i.e. a pattern of mostly positive annual trends at higher stations and negative ones at lower stations. At midaltitudes, the trends are mostly insignificant. Here we hypothesize that the streamflow trends are caused by the following two main processes: on the one hand, melting glaciers produce excess runoff at higher-altitude watersheds. On the other hand, rising temperatures potentially alter hydrological conditions in terms of less snowfall, higher infiltration, enhanced evapotranspiration, etc., which in turn results in decreasing streamflow trends at lower-altitude watersheds. However, these patterns are masked at mid-altitudes because the resulting positive and negative trends balance each other. To support these hypotheses, we attempted to attribute the detected trends to specific causes. For this purpose, we analysed trends of filtered daily streamflow data, as the causes for these changes might be restricted to a smaller temporal scale than the annual one. This allowed for the explicit determination of the exact days of year (DOYs) when certain streamflow trends emerge, which were then linked with the corresponding DOYs of the trends and characteristic dates of other observed variables, e.g. the average DOY when temperature crosses the freezing point in spring. Based on these analyses, an empirical statistical model was derived that was able to simulate daily streamflow trends sufficiently well. Analyses of subdaily streamflow changes provided additional insights. Finally, the present study supports many modelling approaches in the literature which found out that the main drivers of alpine streamflow changes are increased glacial melt, earlier snowmelt and lower snow accumulation in wintertime.