The molecular IrF5−, IrF6− anions and M[IrF6] (M = Na-Cs) ion pairs were prepared by co-deposition of laser-ablated MF with IrF6 and isolated in solid Ne or Ar matrices. The free anions were obtained by co-deposition of IrF6 with laser-ablated metals (Ir, Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for scalar-relativistic and spin-orbit coupling effects as well as multi-reference configuration-interaction approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF6− and its alkali-metal ion pairs. The observed IR bands and the computations show that the IrF6− anion adopts an Oh structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted D4h structure in a triplet ground state as suggested by scalar-relativistic calculations. The corresponding “closed-shell” M[IrF6] ion pairs with C3v symmetry are stabilized by coordination of an alkali metal ion to three F atoms, and their structural change in the series from M = Na to Cs was proven spectroscopically. There is no evidence for the formation of IrF7, IrF7− or M[IrF7] (M = Na-Cs) ion pairs in our experiments.
View lessThe trifluorosilylarsinidene F3SiAs in the triplet ground state has been generated through the reaction of laser-ablated silicon atoms with AsF3 in cryogenic Ne- and Ar-matrices. The reactions proceed with the initial formation perfluorinated arsasilene FAsSiF2 in the singlet ground state by two As‒F bonds insertion reaction on annealing. The trifluorosilylarsinidene F3SiAs was formed via F-migration reactions of FAsSiF2 under irradiation at UV light (λ = 275 nm). The characterization of FAsSiF2 and F3SiAs by IR matrix-isolation spectroscopy is supported by computations at CCSD(T)-F12/aug-cc-pVTZ and B3LYP/aug-cc-pVTZ levels of theory.
View lessHerein we report a general access to silver(i) perfluoroalcoholates, their structure in the solid state and in solution, and their use as transfer reagents. The silver(i) perfluoroalcoholates are prepared by the reaction of AgF with the corresponding perfluorinated carbonyl compounds in acetonitrile and are stable for a prolonged time at –18 °C. X-Ray analysis of single crystals of perfluoroalcoholate species showed that two Ag(i) centers are bridged by the alcoholate ligands. In acetonitrile solution, Ag[OCF3] forms different structures as indicated by IR spectroscopy. Furthermore, the silver(i) perfluoroalcoholates can be used as easy-to-handle transfer reagents for the synthesis of Cu[OCF3], Cu[OC2F5], [PPh4][Au(CF3)3(OCF3)], and fluorinated alkyl ethers.
View lessTriazaphospholes are potential polydentate ligands due to the presence of both phosphorus and nitrogen donor atoms within the aromatic 5-membered heterocycle. The incorporation of an additional pyridyl-substituent opens up the possibility of a post-synthesis modification via chemoselective and also stepwise alkylation exclusively of the nitrogen atoms. This can be controlled by the choice and by the stoichiometry of the electrophile and allows the targeted synthesis of a variety of novel mono- and dicationic ligands. Reaction with Cu(I)-halides causes the formation of cuprates of the type [CuXn](n-1)-, which enables coordination of the π-acidic phosphorus donor to the negatively charged metal core, which is favored over the coordination by a strongly σ-donating nitrogen atom. The use of cationic triazaphosphole derivatives can be used as a strategy to enforce the coordination of the ligand to an electron rich metal solely via the phosphorus atom. However, there is a subtle balance between the formation of either coordination polymers or dimeric structures, as the substitution pattern on the heterocycle and the nature of the halide have a large influence on the coordination motifs formed.
View lessMehr als 30 Jahre nach der Wende scheint der Deutungskampf um das Ende des DDR-Rundfunks nicht beigelegt zu sein. Einerseits werden die mangelnden Einflussmöglichkeiten Ostdeutscher bei der Gestaltung des Rundfunks nach 1989 kritisiert. Andererseits wird die Eingliederung in das westdeutsche Rundfunksystem als Erfolg gefeiert, wobei die verschiedenen Identifikationsmöglichkeiten hervorgehoben werden, die die neu gegründeten Landessender von Anfang an boten. Dieser Beitrag fragt, wie Ostdeutsche den DDR-Rundfunk und seine Abwicklung heute erinnern. Gestützt auf die Strukturations- und Identitätstheorie von Anthony Giddens und auf der Basis von 37 biographischen Interviews wird ein Spektrum von Deutungen aufgezeigt, die Menschen aus Ostberlin rückblickend mit dem Medienstrukturumbruch verbinden. Die Studie zeigt, dass neben einer Gruppe von Befragten, die den späten DDR-Rundfunk kaum oder gar nicht in ihre Selbsterzählungen eingebunden haben, die Vergegenwärtigung dieser Einrichtung über unterschiedliche Biographien hinweg im Modus einer Selbstvergewisserung stattfindet. Dabei werden Zuordnungen und Abgrenzungen zur DDR-Herkunft vorgenommen. Die DDR-Rundfunkgeschichte wird mit Identität aufgeladen, was zum einen auf die medial dominanten DDR- und Ost-Diskurse zurückzuführen ist, zum anderen auf die verschiedenen (Kollektiv‑)Erfahrungen und Lebensbedingungen der Ostdeutschen nach 1989.
View lessAccurate ensemble forecasts of heavy precipitation in India are vital for many applications and essential for early warning of damaging flood events, especially during the monsoon season. In this study we investigate to what extent Quantile Mapping (QM) and Ensemble Model Output Statistics (EMOS) statistical postprocessing reduce errors in precipitation ensemble forecasts over India, in particular for heavy precipitation. Both methods are applied to day-1 forecasts at 12-km resolution from the 23-member National Centre for Medium Range Weather Forecasting (NCMRWF) global ensemble prediction system (NEPS-G). By construction, QM leads to distributions close to the observed ones, while EMOS optimizes the ensemble spread, and it is not a priori clear which is better suited for practical applications. The methods are therefore compared with respect to several key aspects of the forecasts: local distributions, ensemble spread, and skill for forecasting precipitation amounts and the exceedance of heavy-precipitation thresholds. The evaluation includes rank histograms, Continuous Ranked Probability Skill Scores (CRPSS), Brier Skill Scores (BSS), reliability diagrams, and receiver operating characteristic. EMOS performs best not only with respect to correcting under- or overdispersive ensembles, but also in terms of forecast skill for precipitation amounts and heavy precipitation events, with positive CRPSS and BSS in most regions (both up to about 0.4 in some areas), while QM in many regions performs worse than the raw forecast. QM performs best with respect to the overall local precipitation distributions. Which aspects of the forecasts are most relevant depends to some extent on how the forecasts are used. If the main criteria are the correction of under- or overdispersion, forecast reliability, match between the forecasted distribution for individual days and observations (CRPSS), and the skill in forecasting heavy-precipitation events (BSS), then EMOS is the better choice for postprocessing NEPS-G forecasts for short lead times.
View lessThe photothermal therapeutic effect on tumors located at different subcutaneous depths varies due to the attenuation of light by tissue. Here, based on the wavelength-dependent optical attenuation properties of tissues, the tumor depth is assessed using a multichannel lanthanide nanocomposite. A zeolitic imidazolate framework (ZIF-8)-coated nanocomposite is able to deliver high amounts of the hydrophilic heat shock protein 90 inhibitor epigallocatechin gallate through a hydrogen-bonding network formed by the encapsulated highly polarized polyoxometalate guest. It is superior to both bare and PEGylated ZIF-8 for drug delivery. With the assessment of tumor depth and accumulated amount of nanocomposite by fluorescence, an irradiation prescription can be customized to release sufficient HSP90 inhibitor and generate heat for sensitized photothermal treatment of tumors, which not only ensured therapeutic efficacy but also minimized damage to the surrounding tissues.
View lessInternet searches for health-related purposes are common, with search engines like Google being the most popular starting point. However, results on the popularity of health information-seeking behaviors are based on self-report data, often criticized for suffering from incomplete recall, overreporting, and low reliability. Therefore, the current study builds on user-centric tracking of Internet use to reveal how individuals actually behave online. We conducted a secondary analysis of passively recorded Internet use logs to examine the prevalence of health-related search engine use, the types of health information searched for, and the sources visited after the searches. The analysis revealed two key findings. 1) We largely support earlier survey-based findings on the prevalence of online health information seeking with search engines and the relatively minor differences in information-seeking behaviors between socio-demographic groups. 2) We provide a more granular picture of the process of HISB using search engines by identifying different selection patterns depending on the scope of the searches.
View lessThe phytosteroid ecdysterone is classified as an anabolic agent and has been included on the monitoring list of the World Anti-Doping Agency since 2020. Therefore, the consumption of food rich in ecdysterone, such as quinoa and spinach, is the focus of a lively debate. Thus, the urinary excretion of ecdysterone and its metabolites in humans was investigated following quinoa consumption alone and in combination with spinach. Eight participants (four male and four female) were included, and they ingested 368 ± 61 g cooked quinoa alone and in combination with 809 ± 115 g spinach after a washout. Post-administration urines were analyzed by LC-MS/MS. After intake of both preparations, ecdysterone and two metabolites were excreted in the urine. The maximum concentration of ecdysterone ranged from 0.44 to 5.5 µg/mL after quinoa and from 0.34 to 4.1 µg/mL after quinoa with spinach. The total urinary excreted amount as parent drug plus metabolites was 2.61 ± 1.1% following quinoa intake and 1.7 ± 0.9% in combination with spinach. Significant differences were found in the total urinary excreted amount of ecdysterone, 14-deoxy-ecdysterone, and 14-deoxy-poststerone. Only small portions of ecdysterone from quinoa and the combination with spinach were excreted in the urine, suggesting that both quinoa and spinach are poor sources of ecdysterone in terms of bioavailability.
View lessEarly human habitation of the arid to semiarid Central Iranian Plateau was strongly connected to the availability of water and associated natural hazards, such as flooding and drought events. In this geoarchaeological study, we focus on the occupation at the prehistoric site of Ajor Pazi within the formerly active fluvial environment of the Varamin Plain. Through radiocarbon and luminescence-dated sediment cross-sections, we apply multivariate statistics to sedimentological characteristics of bulk samples collected during a rescue excavation in 2018. Based on facies interpretations, we differentiate depositional processes and present their implications for the environs of Ajor Pazi. Our results show evidence of settlement activities between 6.4 and 5.6 ka cal B.P. (4.4–3.6 ka cal. B.C.E.). Phases of reduced geomorphodynamics can be distinguished when soil-forming processes take place. Our findings provide insights into the hitherto scarcely explored Transitional Chalcolithic II period during which the site of Ajor Pazi emerged and began to shape its environs.
View lessSo far, evaluation of training initiatives for dairy farm employees has been limited to the reaction and learning level. The effect of training on dairy farm employees' behavior has not been studied yet. The objective of this study was to determine the effectiveness of online training to change employee behavior toward best-practice routines. An interactive training course related to udder health was developed in 5 modules in Spanish and English: (1) collecting an aseptic milk sample, (2) administering intramammary treatment, (3) deciding on salable milk, (4) treating a cow at dry-off with antibiotics, and (5) administering teat sealants. Participants navigated the modules at their own pace or watched a narrated video. Employees were assessed performing 2 procedures related to dry cow treatment (i.e., treating a cow at dry-off with antibiotics, administering internal teat sealant) by using an objective structured clinical examination. If possible, all employees were scored performing the procedure on 2 cows before and within 2 to 3 wk after the training was applied.
View lessDigital data have become a valuable resource for autocratic governments seeking to influence societal behaviours. The rise of social credit systems in China has garnered a great deal of attention, with some even referring to them as ‘Orwellian’ surveillance systems. This study expands on previous research that has found surprisingly high levels of acceptance of social credit systems in China to the Southeast Asian region. Through an online opinion survey conducted in Thailand, Indonesia, Malaysia and the Philippines, we discovered that citizens in these countries exhibit higher acceptance rates of social credit systems than opposition rates, although lower than those observed in China. Moreover, we find that acceptance rates would decline significantly if the technologies supporting these systems originated from China. By introducing an external technology acceptance model, we provide an explanation for these findings based on citizens' attitudes towards their domestic situation and their perceptions of China's potential benefits to their countries. Interestingly, most of the ‘China Threat’ perceptions do not translate into opposition against Chinese social credit system technologies, except for military risks. Instead, citizens' negative views are primarily influenced by specific technology-related risks. These findings contribute to the existing literature on the acceptance of government-run social credit systems and public perception in the context of international relations.
View lessFamilial socioeconomic background can impact not only academic success, but also the personality of offspring. Yet, there is little evidence on whether it might influence how parents describe their children’s personality. To fill this gap, we used latent multitrait-multimethod (CTCM-1) models to examine familial socioeconomic background as possible predictor of parental perceiver effects regarding their offspring’s personality by contrasting parental assessments against teacher-reports. Study 1 (N = 5,798) investigated reports on elementary school students’ Big Five and Study 2 (N = 3,771) focused on school-related personality facets. Socioeconomic status predicted the parental report in both studies. Participation in high-culture arts incrementally predicted parental report over and above socioeconomic status. Specifically, parents with higher participation in high-culture arts rated their children in a more positive light than class teachers. These background specific perceiver effects might reflect both varying personality judgments or actual differences in behavior.
View lessBenthic graptolites (Graptolithina) were surprisingly common and diverse in the Miaolingian (Cambrian), but have rarely been described in detail. Encrusting and erect growing colonies already evolved and can be differentiated in early Miaolingian faunas. The Rhabdopleuridae with their encrusting colonies provide few fossils, but members of the erect growing, bushy colonies of the Dithecodendridae are more common, at least as fragments indicating considerable fragmentation and transport. In the Wuliuan, the benthic graptolites reached a considerable diversity at the genus level with at least 6 genera appearing in this interval. The most common taxon is the encrusting genus Sphenoecium with its robust colonies, showing a worldwide distribution. Most taxa, however, are known from few records and their biostratigraphical and palaeogeographical distribution cannot be established yet. Erroneously, the widely distributed Tarnagraptus with its conical thecae has often been misidentified as the Ordovician Mastigograptus, but differs considerably in its tubarium construction and both might not be closely related.
View lessMit dem Individualized Classroom Assessment Scoring System (inCLASS) liegt ein Beobachtungsinstrument vor, das zum Ziel hat, Interaktionen in Kitas auf Kindebene erfassen und in ihrer Qualität bestimmen zu können. Der Beitrag geht den Fragen nach, inwieweit das inCLASS diesem Anspruch nach Maßgabe gängiger Gütekriterien gerecht wird und welche Herausforderungen und Limitationen damit verbunden sind. Die Ausführungen stützen sich auf eigene Forschungserfahrungen mit dem Instrument. Über das inCLASS hinaus werden Bezüge zu weiteren Qualitätsmessverfahren (CLASS und KES) hergestellt. Im Ergebnis zeigt das inCLASS einige Stärken und Schwächen. Stärken liegen unter anderem in der forschungsbasierten Ausrichtung auf die Individualebene von Kindern, was es ermöglicht, Verläufe der kindlichen Interaktionsqualität längsschnittlich nachzuzeichnen. Limitationen und Herausforderungen betreffen insbesondere die Faktorenstruktur und die Konfundierung der Erfassung von kindlichen Interaktionen und Kompetenzen.
View lessTaking the example of conspiracy-related communication online as one form of contentious politics, this study examines the data collection challenges for multidimensional comparative research across platforms, time, and cultural embeddings. It compares the architectures and features relevant to data collection, access regimes, and use cultures for a set of digital platforms and communication venues. Differentiating between actor- and content-based strategies, this study discusses the potentials and limitations of these approaches, considering differences in platforms, temporal dynamics, and cultural embeddings as well as several layers of equivalence. The discussion highlights crucial insights into designing data collection strategies in multidimensional comparative studies.
View lessChromatin is a dynamic network that regulates genome organization and gene expression. Different types of chromatin regulators are highly conserved among Archaeplastida, including unicellular algae, while some chromatin genes are only present in land plant genomes. Here, we review recent advances in understanding the function of conserved chromatin factors in basal land plants and algae. We focus on the role of Polycomb-group genes which mediate H3K27me3-based silencing and play a role in balancing gene dosage and regulating haploid-to-diploid transitions by tissue-specific repression of the transcription factors KNOX and BELL in many representatives of the green lineage. Moreover, H3K27me3 predominantly occupies repetitive elements which can lead to their silencing in a unicellular alga and basal land plants, while it covers mostly protein-coding genes in higher land plants. In addition, we discuss the role of nuclear matrix constituent proteins as putative functional lamin analogs that are highly conserved among land plants and might have an ancestral function in stress response regulation. In summary, our review highlights the importance of studying chromatin regulation in a wide range of organisms in the Archaeplastida.
View lessThe objective of this study was to correlate movement assessed by a pyroelectric infrared sensor system in preweaning dairy calves with lying and standing time assessed by a 3D accelerometer considering the temperature-humidity index (THI). A total of 35 dairy calves (1–7 d of age) were enrolled in the study and 20 calves were included in the final analyses. The lying and standing time of the calves was monitored with a 3D accelerometer (Hobo Pendant G Data Logger, Onset Computer Corporation, USA), which was used as the gold standard reference. The infrared sensor monitoring system (IMS; Calf Monitoring System, Futuro Farming GmbH, Germany) was fixed to the fence of the calf hutch within the calf's reach. Temperature-humidity was monitored with 2 validated THI sensors inside and on outside of each calf hutch. Additionally, one THI sensor was located near the calf hutches. The observation period lasted 14 consecutive days. The average standing time assessed by the 3D accelerometer was 13.4 ± 12.7 (mean ± standard deviation) min/h and the average lying time was 46.6 (±12.7) min/h. The median (25th percentile; 75th percentile) number of movements measured by the IMS was 360 (60; 919) movements per hour. Number of movements per hour measured by the IMS was compared with data obtained with a validated 3D accelerometer. The Pearson correlation coefficient between both standing and lying time and the number of movements was r = 0.85 and r = −0.85, respectively. The Pearson correlation coefficients were only slightly influenced by THI (low THI [<68]: r = 0.86; medium THI [68–72]: r = 0.85; high THI [>72]: r = 0.81). Our data show that the number of movements of dairy calves measured by IMS were highly correlated with the chosen gold standard reference method. High THI slightly affects the measurement accuracy of IMS.
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