Unravelling the Role of the Pentafluoroorthotellurate Group as a Ligand in Nickel Chemistry

The pentafluoroorthotellurate group (teflate, OTeF5) is able to form species, for which only the fluoride analogues are known. Despite nickel fluorides being widely investigated, nickel teflates have remained elusive for decades. By reaction of [NiCl4]2− and neat ClOTeF5, we have synthesized the homoleptic [Ni(OTeF5)4]2− anion, which presents a distorted tetrahedral structure, unlike the polymeric [NiF4]2−. This high‐spin complex has allowed the study of the electronic properties of the teflate group, which can be classified as a weak/medium‐field ligand, and therefore behaves as the fluoride analogue also in ligand‐field terms. The teflate ligands in [NEt4]2[Ni(OTeF5)4] are easily substituted, as shown by the formation of [Ni(NCMe)6][OTeF5]2 by dissolving it in acetonitrile. Nevertheless, careful reactions with other conventional ligands have enabled the crystallization of nickel teflate complexes with different coordination geometries, i.e. [NEt4]2[trans‐Ni(OEt2)2(OTeF5)4] or [NEt4][Ni(bpyMe2)(OTeF5)3].Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659Peer Reviewe

Unravelling the Role of the Pentafluoroorthotellurate Group as a Ligand in Nickel Chemistry

The pentafluoroorthotellurate group (teflate, OTeF5) is able to form species, for which only the fluoride analogues are known. Despite nickel fluorides being widely investigated, nickel teflates have remained elusive for decades. By reaction of [NiCl4]2− and neat ClOTeF5, we have synthesized the homoleptic [Ni(OTeF5)4]2− anion, which presents a distorted tetrahedral structure, unlike the polymeric [NiF4]2−. This high‐spin complex has allowed the study of the electronic properties of the teflate group, which can be classified as a weak/medium‐field ligand, and therefore behaves as the fluoride analogue also in ligand‐field terms. The teflate ligands in [NEt4]2[Ni(OTeF5)4] are easily substituted, as shown by the formation of [Ni(NCMe)6][OTeF5]2 by dissolving it in acetonitrile. Nevertheless, careful reactions with other conventional ligands have enabled the crystallization of nickel teflate complexes with different coordination geometries, i.e. [NEt4]2[trans‐Ni(OEt2)2(OTeF5)4] or [NEt4][Ni(bpyMe2)(OTeF5)3]

Quantifying the impact of key factors on the carbon mitigation potential of managed temperate forests

Background: Forests mitigate climate change by reducing atmospheric CO2-concentrations through the carbon sink in the forest and in wood products, and substitution effects when wood products replace carbon-intensive materials and fuels. Quantifying the carbon mitigation potential of forests is highly challenging due to the influence of multiple important factors such as forest age and type, climate change and associated natural disturbances, harvest intensities, wood usage patterns, salvage logging practices, and the carbon-intensity of substituted products. Here, we developed a framework to quantify the impact of these factors through factorial simulation experiments with an ecosystem model at the example of central European (Bavarian) forests. Results: Our simulations showed higher mitigation potentials of young forests compared to mature forests, and similar ones in broad-leaved and needle-leaved forests. Long-lived wood products significantly contributed to mitigation, particularly in needle-leaved forests due to their wood product portfolio, and increased material usage of wood showed considerable climate benefits. Consequently, the ongoing conversion of needle-leaved to more broad-leaved forests should be accompanied by the promotion of long-lived products from broad-leaved species to maintain the product sink. Climate change (especially increasing disturbances) and decarbonization were among the most critical factors influencing mitigation potentials and introduced substantial uncertainty. Nevertheless, until 2050 this uncertainty was narrow enough to derive robust findings. For instance, reducing harvest intensities enhanced the carbon sink in our simulations, but diminished substitution effects, leading to a decreased total mitigation potential until 2050. However, when considering longer time horizons (i.e. until 2100), substitution effects became low enough in our simulations due to expected decarbonization such that decreasing harvests often seemed the more favorable solution. Conclusion: Our results underscore the need to tailor mitigation strategies to the specific conditions of different forest sites. Furthermore, considering substitution effects, and thoroughly assessing the amount of avoided emissions by using wood products, is critical to determine mitigation potentials. While short-term recommendations are possible, we suggest risk diversification and methodologies like robust optimization to address increasing uncertainties from climate change and decarbonization paces past 2050. Finally, curbing emissions reduces the threat of climate change on forests, safeguarding their carbon sink and ecosystem services

Trade-Offs for Climate-Smart Forestry in Europe Under Uncertain Future Climate

Forests mitigate climate change by storing carbon and reducing emissions via substitution effects of wood products. Additionally, they provide many other important ecosystem services (ESs), but are vulnerable to climate change; therefore, adaptation is necessary. Climate-smart forestry combines mitigation with adaptation, whilst facilitating the provision of many ESs. This is particularly challenging due to large uncertainties about future climate. Here, we combined ecosystem modeling with robust multi-criteria optimization to assess how the provision of various ESs (climate change mitigation, timber provision, local cooling, water availability, and biodiversity habitat) can be guaranteed under a broad range of climate futures across Europe. Our optimized portfolios contain 29% unmanaged forests, and implicate a successive conversion of 34% of coniferous to broad-leaved forests (11% vice versa). Coppices practically vanish from Southern Europe, mainly due to their high water requirement. We find the high shares of unmanaged forests necessary to keep European forests a carbon sink while broad-leaved and unmanaged forests contribute to local cooling through biogeophysical effects. Unmanaged forests also pose the largest benefit for biodiversity habitat. However, the increased shares of unmanaged and broad-leaved forests lead to reductions in harvests. This raises the question of how to meet increasing wood demands without transferring ecological impacts elsewhere or enhancing the dependence on more carbon-intensive industries. Furthermore, the mitigation potential of forests depends on assumptions about the decarbonization of other industries and is consequently crucially dependent on the emission scenario. Our findings highlight that trade-offs must be assessed when developing concrete strategies for climate-smart forestry

Automated Indirect Immunofluorescence Evaluation of Antinuclear Autoantibodies on HEp-2 Cells

Indirect immunofluorescence (IIF) on human epithelial (HEp-2) cells is considered as the gold standard screening method for the detection of antinuclear autoantibodies (ANA). However, in terms of automation and standardization, it has not been able to keep pace with most other analytical techniques used in diagnostic laboratories. Although there are already some automation solutions for IIF incubation in the market, the automation of result evaluation is still in its infancy. Therefore, the EUROPattern Suite has been developed as a comprehensive automated processing and interpretation system for standardized and efficient ANA detection by HEp-2 cell-based IIF. In this study, the automated pattern recognition was compared to conventional visual interpretation in a total of 351 sera. In the discrimination of positive from negative samples, concordant results between visual and automated evaluation were obtained for 349 sera (99.4%, kappa = 0.984). The system missed out none of the 272 antibody-positive samples and identified 77 out of 79 visually negative samples (analytical sensitivity/specificity: 100%/97.5%). Moreover, 94.0% of all main antibody patterns were recognized correctly by the software. Owing to its performance characteristics, EUROPattern enables fast, objective, and economic IIF ANA analysis and has the potential to reduce intra- and interlaboratory variability

Liquid Argon Instrumentation and Monitoring in LEGEND-200

LEGEND is the next-generation experiment searching for the neutrinoless double beta decay in $^{76}$Ge. The first stage, LEGEND-200, takes over the cryogenic infrastructure of GERDA at LNGS: an instrumented water tank surrounding a 64 m$^{3}$ liquid argon cryostat. Around 200 kg of Ge detectors will be deployed in the cryostat, with the liquid argon acting as cooling medium, high-purity passive shielding and secondary detection medium. For the latter purpose, a liquid argon instrumentation is developed, based on the system used in GERDA Phase II. Wavelength shifting fibers coated with TPB are arranged in two concentric barrels. Both ends are read out by SiPM arrays. A wavelength shifting reflector surrounds the array in order to enhance the light collection far from the array. The LLAMA is installed in the cryostat to permanently monitor the optical parameters and to provide in-situ inputs for modeling purposes. The design of all parts of the LEGEND-200 LAr instrumentation is presented. An overview of the geometry, operation principle, and off-line data analysis of the LLAMA is shown

Anomalous relaxation and self-organization in non-equilibrium processes

We study thermal relaxation in ordered arrays of coupled nonlinear elements with external driving. We find, that our model exhibits dynamic self-organization manifested in a universal stretched-exponential form of relaxation. We identify two types of self-organization, cooperative and anti-cooperative, which lead to fast and slow relaxation, respectively. We give a qualitative explanation for the behavior of the stretched exponent in different parameter ranges. We emphasize that this is a system exhibiting stretched-exponential relaxation without explicit disorder or frustration.Comment: submitted to PR

Die Deutschlandagenda: zur Darstellung innerdeutscher Themen im Ost-West-Medienvergleich

„So isser, der Ossi“ titelte Der Spiegel am 25.8.2019. Nur vier Tage später erschien in der New York Times ein Artikel von Anna Sauerbrey mit dem Titel „30 Years After Reunification, Germany Is Still Two Countries“. Hierdurch wird beispielhaft dargestellt, dass im dreißigsten Jahr nach dem Mauerfall deutsche BürgerInnen weiterhin in Ossis und Wessis unterteilt werden und die anscheinend mangelhafte deutsche Einheit internationale Beachtung erfährt. Doch ist Deutschland wirklich noch so gespalten? Zahlreiche Studien zeigen, dass sich der Graben zwischen Ost und West verringert. Beispielsweise nähern sich die Arbeitslosenquoten einander immer weiter an und es herrscht eine positive Grundstimmung im Land. Nach wie vor scheinen sich die beiden Teile jedoch voneinander zu unterscheiden; weiterhin ist die Rede von einer „Mauer in den Köpfen“. Bei Wahlumfragen wird herausgestellt, dass Ost- und Westdeutsche ein unterschiedliches Wahlverhalten zeigen und auch die Differenz der Löhne zwischen den neuen und alten Bundesländern ist weiterhin Grundlage der Debatte, wenn es um die Frage der deutschen Einigkeit geht. Die Frage, ob Divergenzen auch medial existieren, ist Grundlage des vorliegenden Forschungsprojekts. Hierbei wird versucht eine Forschungslücke in der Kommunikationswissenschaft zu schließen. Zwar wurden bereits zahlreiche Untersuchungen zur deutschen Medienlandschaft durgeführt, diese fokussieren sich jedoch meist auf die 1990er Jahre oder liegen bereits zehn Jahre oder länger zurück. Ziel ist es die deutsche Presselandschaft auf Konvergenzen und Divergenzen hin zu untersuchen, wobei einerseits betrachtet wird welche Themen behandelt und andererseits, wie diese dargestellt werden. Mit der Annahme der Existenz medialer Teilöffentlichkeiten und strukturgleich abgebildeter heterogener Kommunikationsräume in Deutschland, wurde der Medienraum auf Grundlage des arenatheoretischen Modells der Öffentlichkeit von Tobler (2010) in drei Teilöffentlichkeiten geteilt um festzustellen, wie sehr sich diese thematisch ähneln. So wurde unterschieden zwischen der medialen Teilöffentlichkeit West, bestehend aus Westdeutsche Allgemeine Zeitung, der Rheinischen Post und der Neuen Westfälischen, der medialen Teilöffentlichkeit Ost, bestehend aus der Thüringer Allgemeinen, der Sächsischen Zeitung und der Mitteldeutschen Zeitung und der medialen Teilöffentlichkeit national, aus der Frankfurter Allgemeinen Zeitung und der Süddeutschen Zeitung. Diese acht Tageszeitungen wurden mittels eines Zwei-Methoden-Designs empirisch untersucht. Zuerst wurde eine quantitative Themenfrequenzanalyse durchgeführt, im Anschluss eine qualitative Analyse von Frames. Durch das Prinzip der künstlichen Woche ist eine Cluster-Stichprobe gezogen worden. Es ergab sich ein Sample von N = 3.934 Artikeln. Die Ergebnisse wurden hypothesengeleitet ausgewertet, nach welchen davon ausgegangen wurde, dass Divergenzen zwischen den medialen Teilöffentlichkeiten messbar sind. Zwischen den drei Medienagenden konnte jedoch eine Themenkonvergenz von 71,9% festgestellt werden. Die Rangkorrelationskoeffizienten der behandelten Themen in den drei Teilöffentlichkeiten bestätigen eine Angleichung: Ost und West rs=.744 (p < .001), National und Ost rs=.603 (p < .001), National und West rs=.658 (p < .001). Es liegt demnach eine sehr ähnliche Themensetzung und Presseberichterstattung zwischen den medialen Teilöffentlichkeiten vor. Auch wurde darauf eingegangen, ob sich die Medienagenda- West der nationalen Medienagenda eher angleicht als Letztere der Medienagenda- Ost. Diese Hypothesen lassen sich nicht bestätigen, da sich die Ränge der Teilöffentlichkeiten West und National zwar eher gleichen, Ost und National sich jedoch in Hinblick auf die Häufigkeiten der behandelten Themen ähnlicher sind. In einer zweiten vertiefenden Inhaltsanalyse wurden exemplarisch ein wirtschaftliches und ein politisches Thema (der Diesel-Skandal und Rechtsextremismus, anhand des NSU-Prozesses und der Ereignisse in Chemnitz) herangezogen und auf Medienframes hin untersucht. Die Ergebnisse der Frame-Analyse weisen darauf hin, dass Aussagen zu Divergenzen und Konvergenzen in der Darstellung nur themenabhängig möglich sind und sich nicht verallgemeinern lassen. So wird deutlich, dass in Bezug auf den Dieselskandal starke Divergenzen zwischen den erhobenen Deutungsmustern zu erkennen sind. Zwischen den Teilöffentlichkeiten liegen hierbei überwiegend unterschiedliche Medienframes vor. Entgegen der Annahmen verhalten sich die Medienframes zwischen nationaler und Ost-Ebene eher konvergent, während die zwischen nationaler und West-Ebene eher divergieren. Im Gegensatz dazu kann, bei den Fallbeispielen zum Rechtsextremismus, von größtenteils konvergent existierenden Medienframes zwischen den Ebenen gesprochen werden. Insgesamt kann eine positive Bilanz zur deutschen Presseberichterstattung gezogen werden. Es können zwar einige Divergenzen zwischen den konvergent verlaufenden Medienagenden festgemacht werden, jedoch sind diese weitestgehend regional und strukturell zu begründen. Durch eine hohe inhaltliche Konvergenz zwischen den Teilöffentlichkeiten liegt eine einheitliche Presseberichterstattung in Deutschland vor und es kann nicht von ost- beziehungsweise westspezifischen Medien gesprochen werden.“So isser, der Ossi” was the title of the German magazine Der Spiegel on the 25th of August, meaning “So he is, the East German”. Only four days later, the New York Times published an article by Anna Sauerbrey titled “30 Years After Reunification, Germany Is Still Two Countries“. This example shows that in the thirtieth year after the fall of the Berlin Wall, German citizens are still divided based on whether they come from Eastern or Western Germany, and the seemingly inadequate German unity is receiving international attention. But is Germany still that divided? Various studies show, that both parts of Germany are converging constantly. For instance, the unemployment rates in both are nearly identical, and there is an optimistic mood present within the country. Nevertheless, there seem to be differences; there still is talk of an existing wall within the heads. Citizens of Eastern and Western Germany often show different electoral behaviour in the voting booths and polls. Similarly, the wage gap between the new and old states is often referred to when talking about the question of the German unification. In addition, this research project questions whether such divergences also exist in the media. In this way, the study aims to fill a gap within the literature in this field which has previously been underresearched. Although the German media has been looked at several times in previous investigations, these works are almost all more than a decade old. The ambition of the project is to find out how the German press system is shaped by convergences and divergences nowadays. On the one hand, it tries expose which issues are discussed and on the other how they are referred to. Predicated on the assumption that there are differing communication spaces in Germany that are incongruently made up of public arenas portrayed by the mass media, the study differed between three public spheres using the Arenatheoretical Model of Public Sphere by Tobler (2010). The aim was to find out to what point they resemble each other. This study distinguishes the media-agenda-west, made up of the newspapers Westdeutsche Allgemeine Zeitung, Rheinische Post and Neue Westfälische, the media-agenda-east, including the Thüringer Allgemeine, Sächsische Zeitung and Mitteldeutsche Zeitung and the national media-agenda, containing the Frankfurter Allgemeine Zeitung and the Süddeutsche Zeitung. These eight daily newspapers have been examined through the use of a multiple- method design. First a quantitative issue-frequency-analysis was conducted. Secondly, two inner-German issues were selected to analyse existing convergent and divergent media-frames in a qualitative matter. Following the principle of an artificial week a cluster-sample of N=3.934 was drawn. The results were evaluated through several hypotheses to be able to interpret the media agendas. Between all three of them a convergence of issues of 71.9% was determined. Using a rank correlation coefficient by Spearman, the issues were compared by their order of ranks, showing that they are rather similar: media agendas East and West rs=.704 (p < .001), media agendas National and East rs=.603 (p < .001), media agendas National and West rs=.658 (p < .001), the perfect convergence being one. Thus, the data indicate that there is a unified news coverage within the German press system. It has also been surveyed if the western media agenda is more similar to the national media agenda than the eastern one. This could not be confirmed since the rankings of issues between media agendas in the west and national in Germany equal one another, but a comparison of issues between east and national media agendas show that they are more similar. Following a more deepened content analysis, the framing of two topics were specifically analysed, one concerning the economy and the other politics (on the one hand far-right extremism, represented by the court case of the NSU and the incidents in Chemnitz of summer 2018, and on the other the emissions scandal). The results of the frame-analysis suggest that generalizing statements about divergences and convergences within the portrayal of issues are only possible separately. Furthermore, it is apparent that in terms of the emissions scandal, there are many clearly recognizable divergences between the interpretive patterns. As a whole, there appears to be largely juxta positional content in the media from different public spheres. Unexpectedly, the media frames of the eastern public sphere are more convergent to the national one, while the western public sphere is more divergent to it. Contrastively, the two case examples on far-right extremism show mostly convergent media frames. In conclusion, a positive picture of the German press system seems apparent. While there are some divergences within the convergent media agendas, these can to a great extend be explained through regional and structural differences. Due to a high media convergence between the three separate public spheres analysed in this project, a unified reporting within the German press system appears to exist. To differ between specifically Eastern or Western German media is not possible