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We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.
In older research literature, the prose epics emerging from the court of Elisabeth of Lorraine and Nassau-Saarbrücken have repeatedly been accused of lacking structure and literariness. By contrast, this article shows that narrative principles of seriality generate the complex structure of the voluminous ›Loher und Maller‹: literary strategies of repetition and variation organize the text on different levels. Recurring narrative structures, thematic constellations and motivations as well as lexical stereotypes are part of this comprehensive principle of seriality. Not triviality and insufficiency, but structural and narrative complexity and lexical accumulation of significance characterize ›Loher und Maller‹.
Investigation of processes that contribute to the maintenance of genomic stability is one crucial factor in the attempt to understand mechanisms that facilitate ageing. The DNA damage response (DDR) and DNA repair mechanisms are crucial to safeguard the integrity of DNA and to prevent accumulation of persistent DNA damage. Among them, base excision repair (BER) plays a decisive role. BER is the major repair pathway for small oxidative base modifications and apurinic/apyrimidinic (AP) sites. We established a highly sensitive non-radioactive assay to measure BER incision activity in murine liver samples. Incision activity can be assessed towards the three DNA lesions 8-oxo-2’-deoxyguanosine (8-oxodG), 5-hydroxy-2’-deoxyuracil (5-OHdU), and an AP site analogue. We applied the established assay to murine livers of adult and old mice of both sexes. Furthermore, poly(ADP-ribosyl)ation (PARylation) was assessed, which is an important determinant in DDR and BER. Additionally, DNA damage levels were measured to examine the overall damage levels. No impact of ageing on the investigated endpoints in liver tissue were found. However, animal sex seems to be a significant impact factor, as evident by sex-dependent alterations in all endpoints investigated. Moreover, our results revealed interrelationships between the investigated endpoints indicative for the synergetic mode of action of the cellular DNA integrity maintaining machinery.
Bioturbation contributes to soil formation and ecosystem functioning. With respect to the active transport of matter by voles, bioturbation may be considered as a very dynamic process among those shaping soil formation and biogeochemistry. The present study aimed at characterizing and quantifying the effects of bioturbation by voles on soil water relations and carbon and nitrogen stocks. Bioturbation effects were examined based on a field set up in a luvic arenosol comprising of eight 50 x 50 m enclosures with greatly different numbers of common vole (Microtus arvalis L., ca. 35-150 individuals ha(-1) mth(-1)). Eleven key soil variables were analyzed: bulk density, infiltration rate, saturated hydraulic conductivity, water holding capacity, contents of soil organic carbon (SOC) and total nitrogen (N), CO2 emission potential, C/N ratio, the stable isotopic signatures of C-13 and N-15, and pH. The highest vole densities were hypothesized to cause significant changes in some variables within 21 months. Results showed that land history had still a major influence, as eight key variables displayed an additional or sole influence of topography. However, the delta N-15 at depths of 10-20 and 20-30 cm decreased and increased with increasing vole numbers, respectively. Also the CO2 emission potential from soil collected at a depth of 15-30 cm decreased and the C/N ratio at 5-10 cm depth narrowed with increasing vole numbers. These variables indicated the first influence of voles on the respective mineralization processes in some soil layers. Tendencies of vole activity homogenizing SOC and N contents across layers were not significant. The results of the other seven key variables did not confirm significant effects of voles. Thus overall, we found mainly a first response of variables that are indicative for changes in biogeochemical dynamics but not yet of those representing changes in pools.
In the late Palaeozoic fore-arc system of north-central Chile at latitudes 31-32 degrees S (from the west to the east) three lithotectonic units are telescoped within a short distance by a Mesozoic strikeslip event (derived peak P-T conditions in brackets): (1) the basally accreted Choapa Metamorphic Complex (CMC; 350-430 degrees C, 6-9 kbar), (2) the frontally accreted Arrayan Formation (AF; 280-320 degrees C, 4-6 kbar) and (3) the retrowedge basin of the Huentelauquen Formation (HF; 280-320 degrees C, 3-4 kbar). In the CMC, Ar-Ar spot ages locally date white-mica formation at peak P-T conditions and during early exhumation at 279-242 Ma. In a local garnet mica-schist intercalation (570-585 degrees C, 11-13 kbar) Ar-Ar spot ages refer to the ascent from the subduction channel at 307-274 Ma. Portions of the CMC were isobarically heated to 510-580 degrees C at 6.6-8.5 kbar. The age of peak P-T conditions in the AF can only vaguely be approximated at >= 310 Ma by relict fission-track ages consistent with the observation that frontal accretion occurred prior to basal accretion. Zircon fission-track dating indicates cooling below similar to 280 degrees C at similar to 248 Ma in the CMC and the AF, when a regional unconformity also formed. Ar-Ar white-mica spot ages in parts of the CMC and within the entire AF and HF point to heterogeneous resetting during Mesozoic extensional and shortening events at similar to 245-240 Ma, similar to 210-200 Ma, similar to 174-159 Ma and similar to 142-127 Ma. The zircon fission-track ages are locally reset at 109-96 Ma. All resetting of Ar-Ar white-mica ages is proposed to have occurred by in situ dissolution/precipitation at low temperature in the presence of locally penetrating hydrous fluids. Hence syn-and postaccretionary events in the fore-arc system can still be distinguished and dated in spite of its complex heterogeneous postaccretional overprint.
40Ar/39Ar in situ UV laser ablation of white mica, Rb–Sr mineral isochrons and zircon fission track dating were applied to determine ages of very low- to low-grade metamorphic processes at 3.5±0.4 kbar, 280±30°C in the Avalonian Mira terrane of SE Cape Breton Island (Nova Scotia). The Mira terrane comprises Neoproterozoic volcanic-arc rocks overlain by Cambrian sedimentary rocks. Crystallization of metamorphic white mica was dated in six metavolcanic samples by 40Ar/39Ar spot age peaks between 396±3 and 363±14 Ma. Rb–Sr systematics of minerals and mineral aggregates yielded two isochrons at 389±7 Ma and 365±8 Ma, corroborating equilibrium conditions during very low- to low-grade metamorphism. The dated white mica is oriented parallel to foliations produced by sinistral strike-slip faulting and/or folding related to the Middle–Late Devonian transpressive assembly of Avalonian terranes during convergence and emplacement of the neighbouring Meguma terrane. Exhumation occurred earlier in the NW Mira terrane than in the SE. Transpression was related to the closure of the Rheic Ocean between Gondwana and Laurussia by NW-directed convergence. The 40Ar/39Ar spot age spectra also display relict age peaks at 477–465 Ma, 439 Ma and 420–428 Ma attributed to deformation and fluid access, possibly related to the collision of Avalonia with composite Laurentia or to earlier Ordovician–Silurian rifting. Fission track ages of zircon from Mira terrane samples range between 242±18 and 225±21 Ma and reflect late Palaeozoic reburial and reheating close to previous peak metamorphic temperatures under fluid-absent conditions during rifting prior to opening of the Central Atlantic Ocean.
Concurrent observation technologies have made high-precision real-time data available in large quantities. Data assimilation (DA) is concerned with how to combine this data with physical models to produce accurate predictions. For spatial-temporal models, the ensemble Kalman filter with proper localisation techniques is considered to be a state-of-the-art DA methodology. This article proposes and investigates a localised ensemble Kalman Bucy filter for nonlinear models with short-range interactions. We derive dimension-independent and component-wise error bounds and show the long time path-wise error only has logarithmic dependence on the time range. The theoretical results are verified through some simple numerical tests.
German football stadiums are well known for their atmosphere. It is often described as ‘electrifying,’ or ‘cracking.’ This article focuses on this atmosphere. Using a phenomenological approach, it explores how this emotionality can be understood and how geography matters while attending a match. Atmosphere in this context is conceptualized based on work by as a mood-charged space, neither object- nor subject-centered, but rather a medium of perception which cannot not exist. Based on qualitative research done in the home stadium of Hertha BSC in the German Bundesliga, this article shows that the bodily sensations experienced by spectators during a visit to the stadium are synchronized with events on the pitch and with the more or less imposing scenery. The analysis of in situ diaries reveals that spectators experience a comprehensive sense of collectivity. The study presents evidence that the occurrence of these bodily sensations is strongly connected with different aspects of spatiality. This includes sensations of constriction and expansion within the body, an awareness of one’s location within the stadium, the influence of the immediate surroundings and cognitive here/there and inside/outside distinctions.
In intervention research, single-case experimental designs are an important way to gain insights into the causes of individual changes that yield high internal validity. They are commonly applied to examine the effectiveness of classroom-based interventions to reduce problem behavior in schools. At the same time, there is no consensus on good design characteristics of single-case experimental designs when dealing with behavioral problems in schools. Moreover, specific challenges arise concerning appropriate approaches to analyzing behavioral data. Our study addresses the interplay between the test power of piecewise regression analysis and important design specifications of single-case research designs. Here, we focus on the influence of the following specifications of single-case research designs: number of measurement times, the initial frequency of the behavior, intervention effect, and data trend. We conducted a Monte-Carlo study. First, simulated datasets were created with specific design conditions based on reviews of published single-case intervention studies. Following, data were analyzed using piecewise Poisson-regression models, and the influence of specific design specifications on the test power was investigated. Our results indicate that piecewise regressions have a high potential of adequately identifying the effects of interventions for single-case studies. At the same time, test power is strongly related to the specific design specifications of the single-case study: Few measurement times, especially in phase A, and low initial frequencies of the behavior make it impossible to detect even large intervention effects. Research designs with a high number of measurement times show robust power. The insights gained are highly relevant for researchers in the field, as decisions during the early stage of conceptualizing and planning single-case experimental design studies may impact the chance to identify an existing intervention effect during the research process correctly.
Sphingolipids are a class of lipids that share a sphingoid base backbone. They exert various effects in eukaryotes, ranging from structural roles in plasma membranes to cellular signaling. De novo sphingolipid synthesis takes place in the endoplasmic reticulum (ER), where the condensation of the activated C₁₆ fatty acid palmitoyl-CoA and the amino acid L-serine is catalyzed by serine palmitoyltransferase (SPT). The product, 3-ketosphinganine, is then converted into more complex sphingolipids by additional ER-bound enzymes, resulting in the formation of ceramides. Since sphingolipid homeostasis is crucial to numerous cellular functions, improved assessment of sphingolipid metabolism will be key to better understanding several human diseases. To date, no assay exists capable of monitoring de novo synthesis sphingolipid in its entirety. Here, we have established a cell-free assay utilizing rat liver microsomes containing all the enzymes necessary for bottom-up synthesis of ceramides. Following lipid extraction, we were able to track the different intermediates of the sphingolipid metabolism pathway, namely 3-ketosphinganine, sphinganine, dihydroceramide, and ceramide. This was achieved by chromatographic separation of sphingolipid metabolites followed by detection of their accurate mass and characteristic fragmentations through high-resolution mass spectrometry and tandem-mass spectrometry. We were able to distinguish, unequivocally, between de novo synthesized sphingolipids and intrinsic species, inevitably present in the microsome preparations, through the addition of stable isotope-labeled palmitate-d₃ and L-serine-d₃. To the best of our knowledge, this is the first demonstration of a method monitoring the entirety of ER-associated sphingolipid biosynthesis. Proof-of-concept data was provided by modulating the levels of supplied cofactors (e.g., NADPH) or the addition of specific enzyme inhibitors (e.g., fumonisin B₁). The presented microsomal assay may serve as a useful tool for monitoring alterations in sphingolipid de novo synthesis in cells or tissues. Additionally, our methodology may be used for metabolism studies of atypical substrates – naturally occurring or chemically tailored – as well as novel inhibitors of enzymes involved in sphingolipid de novo synthesis.
This paper discusses a hitherto undescribed usage of the particle so as a dedicated focus marker in contemporary German. I discuss grammatical and pragmatic characteristics of this focus marker, supporting my account with natural linguistic data and with controlled experimental evidence showing that so has a significant influence on speakers’ understanding of what the focus expression in a sentence is. Against this background, I sketch a possible pragmaticalization path from referential usages of so via hedging to a semantically bleached focus marker, which, unlike particles such as auch ‘also’/‘too’ or nur ‘only’, does not contribute any additional meaning.
This article investigates a public debate in Germany that put a special spotlight on the interaction of standard language ideologies with social dichotomies, centering on the question of whether Kiezdeutsch, a new way of speaking in multilingual urban neighbourhoods, is a legitimate German dialect. Based on a corpus of emails and postings to media websites, I analyse central topoi in this debate and an underlying narrative on language and identity. Central elements of this narrative are claims of cultural elevation and cultural unity for an idealised standard language High German', a view of German dialects as part of a national folk culture, and the construction of an exclusive in-group of German' speakers who own this language and its dialects. The narrative provides a potent conceptual frame for the Othering of Kiezdeutsch and its speakers, and for the projection of social and sometimes racist deliminations onto the linguistic plane.
Rain fall-runoff response in temperate humid headwater catchments is mainly controlled by hydrolo gical processes at the hillslope scale. Applied tracer experiments with fluore scent dye and salt tracers are well known tools in groundwater studies at the large scale and vadose zone studies at the plot scale, where they provide a means to characterise subsurface flow. We extend this approach to the hillslope scale to investigate saturated and unsaturated flow path s concertedly at a forested hill slope in the Austrian Alps. Dye staining experiments at the plot scale revealed that crack s and soil pipe s function as preferential flow path s in the fine-textured soils of the study area, and these preferenti al flow structures were active in fast subsurface transport of tracers at the hillslope scale. Breakthrough curves obtained under steady flow conditions could be fitted well to a one-dimensional convection-dispersion model. Under natural rain fall a positive correlation of tracer concentrations to the transient flows was observed. The results of this study demon strate qualitative and quantitative effects of preferential flow feature s on subsurface stormflow in a temperate humid headwater catchment. It turn s out that , at the hill slope scale, the interaction s of structures and processes are intrinsically complex, which implies that attempts to model such a hillslope satisfactorily require detailed investigation s of effective structures and parameters at the scale of interest.
Previous research on the interplay between static manual postures and visual attention revealed enhanced visual selection near the hands (near-hand effect). During active movements there is also superior visual performance when moving toward compared to away from the stimulus (direction effect). The "modulated visual pathways" hypothesis argues that differential involvement of magno- and parvocellular visual processing streams causes the near-hand effect. The key finding supporting this hypothesis is an increase in temporal and a reduction in spatial processing in near-hand space (Gozli et al., 2012). Since this hypothesis has, so far, only been tested with static hand postures, we provide a conceptual replication of Gozli et al.'s (2012) result with moving hands, thus also probing the generality of the direction effect. Participants performed temporal or spatial gap discriminations while their right hand was moving below the display. In contrast to Gozli et al (2012), temporal gap discrimination was superior at intermediate and not near hand proximity. In spatial gap discrimination, a direction effect without hand proximity effect suggests that pragmatic attentional maps overshadowed temporal/spatial processing biases for far/near-hand space.
Many studies demonstrated interactions between number processing and either spatial codes (effects of spatial-numerical associations) or visual size-related codes (size-congruity effect). However, the interrelatedness of these two number couplings is still unclear. The present study examines the simultaneous occurrence of space- and size-numerical congruency effects and their interactions both within and across trials, in a magnitude judgment task physically small or large digits were presented left or right from screen center. The reaction times analysis revealed that space- and size-congruency effects coexisted in parallel and combined additively. Moreover, a selective sequential modulation of the two congruency effects was found. The size-congruency effect was reduced after size incongruent trials. The space-congruency effect, however, was only affected by the previous space congruency. The observed independence of spatial-numerical and within magnitude associations is interpreted as evidence that the two couplings reflect Different attributes of numerical meaning possibly related to orginality and cardinality.
Deep into the second half of the twentieth century the traditionalist definition of India as a country of villages remained dominant in official political rhetoric as well as cultural production. In the past two decades or so, this ruralist paradigm has been effectively superseded by a metropolitan imaginary in which the modern, globalised megacity increasingly functions as representative of India as a whole. Has the village, then, entirely vanished from the cultural imaginary in contemporary India? Addressing economic practices from upper-class consumerism to working-class family support strategies, this paper attempts to trace how ‘the village’ resurfaces or survives as a cultural reference point in the midst of the urban.
Rezensiertes Werk:
George, Rosemary Marangoly, Indian English and the Fiction of National Literature - Cambridge: Cambridge University Press, 2013. - Hb. viii, 285 pp. - (Zeitschrift für Anglistik und Amerikanistik ; 62(4)) ISBN 978-1-107-04000-7.
Objective: Alexithymia relates to difficulties recognizing and describing emotions. It has been linked to subjectively increased interoceptive awareness (IA) and to psychiatric illnesses such as major depressive disorder (MDD) and somatization. MDD in turn is characterized by aberrant emotion processing and IA on the subjective as well as on the neural level. However, a link between neural activity in response to IA and alexithymic traits in health and depression remains unclear.
Methods: A well-established fMRI task was used to investigate neural activity during IA (heartbeat counting) and exteroceptive awareness (tone counting) in non-psychiatric controls (NC) and MDD. Firstly, comparing MDD and NC, a linear relationship between IA-related activity and scores of the Toronto Alexithymia Scale (TAS) was investigated through whole-brain regression. Secondly, NC were divided by median-split of TAS scores into groups showing low (NC-low) or high (NC-high) alexithymia. MDD and NC-high showed equally high TAS scores. Subsequently, IA-related neural activity was compared on a whole-brain level between the three independent samples (MDD, NC-low, NC-high).
Results: Whole-brain regressions between MDD and NC revealed neural differences during IA as a function of TAS-DD (subscale difficulty describing feelings) in the supragenual anterior cingulate cortex (sACC; BA 24/32), which were due to negative associations between TAS-DD and IA-related activity in NC. Contrasting NC subgroups after median-split on a whole-brain level, high TAS scores were associated with decreased neural activity during IA in the sACC and increased insula activity. Though having equally high alexithymia scores, NC-high showed increased insula activity during IA compared to MDD, whilst both groups showed decreased activity in the sACC.
Conclusions: Within the context of decreased sACC activity during IA in alexithymia (NC-high and MDD), increased insula activity might mirror a compensatory mechanism in NC-high, which is disrupted in MDD.