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Historical narratives play an important role in constructing contemporary notions of citizenship. They are sites on which ideas of the nation are not only reaffirmed but also contested and reframed. In contemporary Germany, dominant narratives of the country’s modern history habitually focus on the legacy of the Third Reich and tend to marginalize the country’s rich and highly complex histories of immigration. The article addresses this commemorative void in relation to Berlin’s urban landscape. It explores how the city’s multilayered architecture provides locations for the articulation of marginal memories—and hence sites of urban citizenship—that are often denied to immigrant communities on a national scale. Through a detailed examination of a small celebration in 1965 that marked the anniversary of the founding of the modern Turkish republic, the article engages with the layers of history that coalesce around such sites in Berlin.
‘Hasty observations’?
(2018)
This article examines geographical field research in Albania and Montenegro under Austro-Hungarian occupation, which lasted from 1916 to 1918. It focusses on one of the most important German-speaking geographers of the early 20 th century, Eugen Oberhummer (1859–1944), a pupil of Friedrich Ratzel, the founder of German geo-politics. In 1917 and 1918, Oberhummer went on two expeditions to Montenegro and Albania during the First World War. He already had travelled in four continents and vaguely knew the Western Balkans from an expedition in 1907. It will be argued that the actual situation in Albania and Montenegro did not alter, but did rather reinforce Oberhummer’s attitudes and opinions on the ‘other’ he encountered. Thus, the two war expeditions – Oberhummer primarily met high-ranking Austro-Hungarian officials and only few locals – confirmed his expectations basing on his ‘Ratzelian’ theoretical conceptions. It will further be argued that – in contrast to the much younger and less experienced ‘scholars-at-arms’ of the expedition of 1916 – war and violence were of secondary relevance for the well-travelled and renowned professor of geography in his late 50s. Neither in Oberhummer’s articles nor in his diaries the war and the occupation of Albania and Montenegro made up an important part. In Oberhummer’s ‘Ratzelian’ view, humans could not change or over-come the basic features of geography, as humans were clearly subordinated to the elemental forces of geography. People, over generations, adapted to geography, not the other way round. The on-going First World War was an opportunity for Oberhummer to travel to Albania and Montenegro, but the guerrilla warfare in large parts of Montenegro, the violence against the civilian population, and the fighting at the Albanian front were of secondary relevance and interest for him. Nevertheless, what Oberhummer observed offers great insights into the Austro-Hungarian occupation of Montenegro and Albania from the perspective of a renowned and – given the general circumstances – pleasantly relaxed Ratzelian geographer at the height of his academic career.
WRKY23 is a component of the transcriptional network mediating auxin feedback on PIN polarity
(2018)
Auxin is unique among plant hormones due to its directional transport that is mediated by the polarly distributed PIN auxin transporters at the plasma membrane. The canalization hypothesis proposes that the auxin feedback on its polar flow is a crucial, plant-specific mechanism mediating multiple self-organizing developmental processes. Here, we used the auxin effect on the PIN polar localization in Arabidopsis thaliana roots as a proxy for the auxin feedback on the PIN polarity during canalization. We performed microarray experiments to find regulators of this process that act downstream of auxin. We identified genes that were transcriptionally regulated by auxin in an AXR3/IAA17-and ARF7/ARF19-dependent manner. Besides the known components of the PIN polarity, such as PID and PIP5K kinases, a number of potential new regulators were detected, among which the WRKY23 transcription factor, which was characterized in more detail. Gain-and loss-of-function mutants confirmed a role for WRKY23 in mediating the auxin effect on the PIN polarity. Accordingly, processes requiring auxin-mediated PIN polarity rearrangements, such as vascular tissue development during leaf venation, showed a higher WRKY23 expression and required the WRKY23 activity. Our results provide initial insights into the auxin transcriptional network acting upstream of PIN polarization and, potentially, canalization-mediated plant development.
We report two corpus analyses to examine the impact of animacy, definiteness, givenness and type of referring expression on the ordering of double objects in the spontaneous speech of German-speaking two- to four-year-old children and the child-directed speech of their mothers. The first corpus analysis revealed that definiteness, givenness and type of referring expression influenced word order variation in child language and child-directed speech when the type of referring expression distinguished between pronouns and lexical noun phrases. These results correspond to previous child language studies in English (e.g., de Marneffe et al. 2012). Extending the scope of previous studies, our second corpus analysis examined the role of different pronoun types on word order. It revealed that word order in child language and child-directed speech was predictable from the types of pronouns used. Different types of pronouns were associated with different sentence positions but also showed a strong correlation to givenness and definiteness. Yet, the distinction between pronoun types diminished the effects of givenness so that givenness had an independent impact on word order only in child-directed speech but not in child language. Our results support a multi-factorial approach to word order in German. Moreover, they underline the strong impact of the type of referring expression on word order and suggest that it plays a crucial role in the acquisition of the factors influencing word order variation.
Ismar Elbogen (1874–1943) and Franz Rosenzweig (1886-1929) were both pioneers in Jewish thought and culture. Elbogen authored the most comprehensive study on Jewish liturgy, while Rosenzweig’s magnum opus The Star of Redemption has emerged as one of the twentieth century’s most innovative and elusive works of Jewish thought. Even though Rosenzweig is not known for his work on or appreciation for the Wissenschaft des Judentums, this article will explore this overlooked aspect of his thought by exploring the influence of Ismar Elbogen. Commentaries to Rosenzweig’s views on prayer are numerous, yet none mention the work of Elbogen. This is a problem. By comparing Elbogen’s work on Jewish liturgy with Rosenzweig’s writings on prayer in the Star, we are able to demonstrate how methods seminal to the Wissenschaft des Judentums helped articulate several of Rosenzweig’s most innovative contributions to Jewish thought.
Why choice matters
(2018)
Measures of democracy are in high demand. Scientific and public audiences use them to describe political realities and to substantiate causal claims about those realities. This introduction to the thematic issue reviews the history of democracy measurement since the 1950s. It identifies four development phases of the field, which are characterized by three recurrent topics of debate: (1) what is democracy, (2) what is a good measure of democracy, and (3) do our measurements of democracy register real-world developments? As the answers to those questions have been changing over time, the field of democracy measurement has adapted and reached higher levels of theoretical and methodological sophistication. In effect, the challenges facing contemporary social scientists are not only limited to the challenge of constructing a sound index of democracy. Today, they also need a profound understanding of the differences between various measures of democracy and their implications for empirical applications. The introduction outlines how the contributions to this thematic issue help scholars cope with the recurrent issues of conceptualization, measurement, and application, and concludes by identifying avenues for future research.
Previous research informs us about facilitators of employees’ promotive voice. Yet little is known about what determines whether a specific idea for constructive change brought up by an employee will be approved or rejected by a supervisor. Drawing on interactionist theories of motivation and personality, we propose that a supervisor will be least likely to support an idea when it threatens the supervisor’s power motive, and when it is perceived to serve the employee’s own striving for power. The prosocial versus egoistic intentions attributed to the idea presenter are proposed to mediate the latter effect. We conducted three scenario-based studies in which supervisors evaluated fictitious ideas voiced by employees that – if implemented – would have power-related consequences for them as a supervisor. Results show that the higher a supervisors’ explicit power motive was, the less likely they were to support a power-threatening idea (Study 1, N = 60). Moreover, idea support was less likely when this idea was proposed by an employee that was described as high (rather than low) on power motivation (Study 2, N = 79); attributed prosocial intentions mediated this effect. Study 3 (N = 260) replicates these results.
This study analyzes the influence of local and regional climatic factors on the stable isotopic composition of rainfall in the Vietnamese Mekong Delta (VMD) as part of the Asian monsoon region. It is based on 1.5 years of weekly rainfall samples. In the first step, the isotopic composition of the samples is analyzed by local meteoric water lines (LMWLs) and single-factor linear correlations. Additionally, the contribution of several regional and local factors is quantified by multiple linear regression (MLR) of all possible factor combinations and by relative importance analysis. This approach is novel for the interpretation of isotopic records and enables an objective quantification of the explained variance in isotopic records for individual factors. In this study, the local factors are extracted from local climate records, while the regional factors are derived from atmospheric backward trajectories of water particles. The regional factors, i.e., precipitation, temperature, relative humidity and the length of backward trajectories, are combined with equivalent local climatic parameters to explain the response variables delta O-18, delta H-2, and d-excess of precipitation at the station of measurement.
The results indicate that (i) MLR can better explain the isotopic variation in precipitation (R-2 = 0.8) compared to single-factor linear regression (R-2 = 0.3); (ii) the isotopic variation in precipitation is controlled dominantly by regional moisture regimes (similar to 70 %) compared to local climatic conditions (similar to 30 %); (iii) the most important climatic parameter during the rainy season is the precipitation amount along the trajectories of air mass movement; (iv) the influence of local precipitation amount and temperature is not sig-nificant during the rainy season, unlike the regional precipitation amount effect; (v) secondary fractionation processes (e.g., sub-cloud evaporation) can be identified through the d-excess and take place mainly in the dry season, either locally for delta O-18 and delta H-2, or along the air mass trajectories for d-excess. The analysis shows that regional and local factors vary in importance over the seasons and that the source regions and transport pathways, and particularly the climatic conditions along the pathways, have a large influence on the isotopic composition of rainfall. Although the general results have been reported qualitatively in previous studies (proving the validity of the approach), the proposed method provides quantitative estimates of the controlling factors, both for the whole data set and for distinct seasons. Therefore, it is argued that the approach constitutes an advancement in the statistical analysis of isotopic records in rainfall that can supplement or precede more complex studies utilizing atmospheric models. Due to its relative simplicity, the method can be easily transferred to other regions, or extended with other factors.
The results illustrate that the interpretation of the isotopic composition of precipitation as a recorder of local climatic conditions, as for example performed for paleorecords of water isotopes, may not be adequate in the southern part of the Indochinese Peninsula, and likely neither in other regions affected by monsoon processes. However, the presented approach could open a pathway towards better and seasonally differentiated reconstruction of paleoclimates based on isotopic records.
Virtual 3D city models represent and integrate a variety of spatial data and georeferenced data related to urban areas. With the help of improved remote-sensing technology, official 3D cadastral data, open data or geodata crowdsourcing, the quantity and availability of such data are constantly expanding and its quality is ever improving for many major cities and metropolitan regions. There are numerous fields of applications for such data, including city planning and development, environmental analysis and simulation, disaster and risk management, navigation systems, and interactive city maps.
The dissemination and the interactive use of virtual 3D city models represent key technical functionality required by nearly all corresponding systems, services, and applications. The size and complexity of virtual 3D city models, their management, their handling, and especially their visualization represent challenging tasks. For example, mobile applications can hardly handle these models due to their massive data volume and data heterogeneity. Therefore, the efficient usage of all computational resources (e.g., storage, processing power, main memory, and graphics hardware, etc.) is a key requirement for software engineering in this field. Common approaches are based on complex clients that require the 3D model data (e.g., 3D meshes and 2D textures) to be transferred to them and that then render those received 3D models. However, these applications have to implement most stages of the visualization pipeline on client side. Thus, as high-quality 3D rendering processes strongly depend on locally available computer graphics resources, software engineering faces the challenge of building robust cross-platform client implementations.
Web-based provisioning aims at providing a service-oriented software architecture that consists of tailored functional components for building web-based and mobile applications that manage and visualize virtual 3D city models. This thesis presents corresponding concepts and techniques for web-based provisioning of virtual 3D city models. In particular, it introduces services that allow us to efficiently build applications for virtual 3D city models based on a fine-grained service concept. The thesis covers five main areas:
1. A Service-Based Concept for Image-Based Provisioning of
Virtual 3D City Models It creates a frame for a broad range of services related to the rendering and image-based dissemination of virtual 3D city models.
2. 3D Rendering Service for Virtual 3D City Models This service provides efficient, high-quality 3D rendering functionality for virtual 3D city models. In particular, it copes with requirements such as standardized data formats, massive model texturing, detailed 3D geometry, access to associated feature data, and non-assumed frame-to-frame coherence for parallel service requests. In addition, it supports thematic and artistic styling based on an expandable graphics effects library.
3. Layered Map Service for Virtual 3D City Models It generates a map-like representation of virtual 3D city models using an oblique view. It provides high visual quality, fast initial loading times, simple map-based interaction and feature data access. Based on a configurable client framework, mobile and web-based applications for virtual 3D city models can be created easily.
4. Video Service for Virtual 3D City Models It creates and synthesizes videos from virtual 3D city models. Without requiring client-side 3D rendering capabilities, users can create camera paths by a map-based user interface, configure scene contents, styling, image overlays, text overlays, and their transitions. The service significantly reduces the manual effort typically required to produce such videos. The videos can automatically be updated when the underlying data changes.
5. Service-Based Camera Interaction It supports task-based 3D camera interactions, which can be integrated seamlessly into service-based visualization applications. It is demonstrated how to build such web-based interactive applications for virtual 3D city models using this camera service.
These contributions provide a framework for design, implementation, and deployment of future web-based applications, systems, and services for virtual 3D city models. The approach shows how to decompose the complex, monolithic functionality of current 3D geovisualization systems into independently designed, implemented, and operated service- oriented units. In that sense, this thesis also contributes to microservice architectures for 3D geovisualization systems—a key challenge of today’s IT systems engineering to build scalable IT solutions.
Water at α-alumina surfaces
(2018)
The (0001) surface of α-Al₂O₃ is the most stable surface cut under UHV conditions and was studied by many groups both theoretically and experimentally. Reaction barriers computed with GGA functionals are known to be underestimated. Based on an example reaction at the (0001) surface, this work seeks to improve this rate by applying a hybrid functional method and perturbation theory (LMP2) with an atomic orbital basis, rather than a plane wave basis. In addition to activation barriers, we calculate the stability and vibrational frequencies of water on the surface. Adsorption energies were compared to PW calculations and confirmed PBE+D2/PW stability results. Especially the vibrational frequencies with the B3LYP hybrid functional that have been calculated for the (0001) surface are in good agreement with experimental findings. Concerning the barriers and the reaction rate constant, the expectations are fully met. It could be shown that recalculation of the transition state leads to an increased barrier, and a decreased rate constant when hybrid functionals or LMP2 are applied.
Furthermore, the molecular beam scattering of water on (0001) surface was studied. In a previous work by Hass the dissociation was studied by AIMD of molecularly adsorbed water, referring to an equilibrium situation. The experimental method to obtaining this is pinhole dosing. In contrast to this earlier work, the dissociation process of heavy water that is brought onto the surface from a molecular beam source was modeled in this work by periodic ab initio molecular dynamics simulations. This experimental method results in a non-equilibrium situation. The calculations with different surface and beam models allow us to understand the results of the non-equilibrium situation better. In contrast to a more equilibrium situation with pinhole dosing, this gives an increase in the dissociation probability, which could be explained and also understood mechanistically by those calculations.
In this work good progress was made in understanding the (1120) surface of α-Al₂O₃ in contact with water in the low-coverage regime. This surface cut is the third most stable one under UHV conditions and has not been studied to a great extent yet. After optimization of the clean, defect free surface, the stability of different adsorbed species could be classified. One molecular minimum and several dissociated species could be detected. Starting from these, reaction rates for various surface reactions were evaluated. A dissociation reaction was shown to be very fast because the molecular minimum is relatively unstable, whereas diffusion reactions cover a wider range from fast to slow. In general, the (112‾0) surface appears to be much more reactive against water than the (0001) surface. In addition to reactivity, harmonic vibrational frequencies were determined for comparison with the findings of the experimental “Interfacial Molecular Spectroscopy” group from Fritz-Haber institute in Berlin. Especially the vibrational frequencies of OD species could be assigned to vibrations from experimental SFG spectra with very good agreement. Also, lattice vibrations were studied in close collaboration with the experimental partners. They perform SFG spectra at very low frequencies to get deep into the lattice vibration region. Correspondingly, a bigger slab model with greater expansion perpendicular to the surface was applied, considering more layers in the bulk. Also with the lattice vibrations we could obtain reasonably good agreement in terms of energy differences between the peaks.
A comprehensive hydro-sedimentological dataset for the Isábena catchment, northeastern (NE) Spain, for the period 2010–2018 is presented to analyse water and sediment fluxes in a Mediterranean mesoscale catchment. The dataset includes rainfall data from 12 rain gauges distributed within the study area complemented by meteorological data of 12 official meteo-stations. It comprises discharge data derived from water stage measurements as well as suspended sediment concentrations (SSCs) at six gauging stations of the River Isábena and its sub-catchments. Soil spectroscopic data from 351 suspended sediment samples and 152 soil samples were collected to characterize sediment source regions and sediment properties via fingerprinting analyses. The Isábena catchment (445 km 2 ) is located in the southern central Pyrenees ranging from 450 m to 2720 m a.s.l.; together with a pronounced topography, this leads to distinct temperature and precipitation gradients. The River Isábena shows marked discharge variations and high sediment yields causing severe siltation problems in the downstream Barasona Reservoir. The main sediment source is badland areas located on Eocene marls that are well connected to the river network. The dataset features a comprehensive set of variables in a high spatial and temporal resolution suitable for the advanced process understanding of water and sediment fluxes, their origin and connectivity and sediment budgeting and for the evaluation and further development of hydro-sedimentological models in
Mediterranean mesoscale mountainous catchments.
Analysis of social media using digital methods is a flourishing approach. However, the relatively easy availability of data collected via platform application programming interfaces has arguably led to the predominance of single-platform research of social media. Such research has also privileged the role of text in social media analysis, as a form of data that is more readily gathered and searchable than images. In this paper, we challenge both of these prevailing forms of social media research by outlining a methodology for visual cross-platform analysis (VCPA), defined as the study of still and moving images across two or more social media platforms. Our argument contains three steps. First, we argue that cross-platform analysis addresses a gap in research methods in that it acknowledges the interplay between a social phenomenon under investigation and the medium within which it is being researched, thus illuminating the different affordances and cultures of web platforms. Second, we build on the literature on multimodal communication and platform vernacular to provide a rationale for incorporating the visual into cross-platform analysis. Third, we reflect on an experimental cross-platform analysis of images within social media posts (n = 471,033) used to communicate climate change to advance different modes of macro- and meso-levels of analysis that are natively visual: image-text networks, image plots and composite images. We conclude by assessing the research pathways opened up by VCPA, delineating potential contributions to empirical research and theory and the potential impact on practitioners of social media communication.
Time-dependent correlation function based methods to study optical spectroscopy involving electronic transitions can be traced back to the work of Heller and coworkers. This intuitive methodology can be expected to be computationally efficient and is applied in the current work to study the vibronic absorption, emission, and resonance Raman spectra of selected organic molecules. Besides, the "non-standard" application of this approach to photoionization processes is also explored. The application section consists of four chapters as described below.
In Chapter 4, the molar absorptivities and vibronic absorption/emission spectra of perylene and several of its N-substituted derivatives are investigated. By systematically varying the number and position of N atoms, it is shown that the presence of nitrogen heteroatoms has a negligible effect on the molecular structure and geometric distortions upon electronic transitions, while spectral properties are more sensitive: In particular the number of N atoms is important while their position is less decisive. Thus, N-substitution can be used to fine-tune the optical properties of perylene-based molecules.
In Chapter 5, the same methods are applied to study the vibronic absorption/emission and resonance Raman spectra of a newly synthesized donor-acceptor type molecule. The simulated absorption/emission spectra agree fairly well with experimental data, with discrepancies being attributed to solvent effects. Possible modes which may dominate the fine-structure in the vibronic spectra are proposed by analyzing the correlation function with the aid of Raman and resonance Raman spectra.
In the next two chapters, besides the above types of spectra, the methods are extended to study photoelectron spectra of several small diamondoid-related systems (molecules, radicals, and cations). Comparison of the photoelectron spectra with available experimental data suggests that the correlation function based approach can describe ionization processes reasonably well. Some of these systems, cationic species in particular, exhibit somewhat peculiar optical behavior, which presents them as possible candidates for functional devices.
Correlation function based methods in a more general sense can be very versatile. In fact, besides the above radiative processes, formulas for non-radiative processes such as internal conversion have been derived in literature. Further implementation of the available methods is among our next goals.
With the growing size and use of night light time series from the Visible Infrared Imaging Radiometer Suite Day/Night Band (DNB), it is important to understand the stability of the dataset. All satellites observe differences in pixel values during repeat observations. In the case of night light data, these changes can be due to both environmental effects and changes in light emission. Here we examine the stability of individual locations of particular large scale light sources (e.g., airports and prisons) in the monthly composites of DNB data from April 2012 to September 2017. The radiances for individual pixels of most large light emitters are approximately normally distributed, with a standard deviation of typically 15-20% of the mean. Greenhouses and flares, however, are not stable sources. We observe geospatial autocorrelation in the monthly variations for nearby sites, while the correlation for sites separated by large distances is small. This suggests that local factors contribute most to the variation in the pixel radiances and furthermore that averaging radiances over large areas will reduce the total variation. A better understanding of the causes of temporal variation would improve the sensitivity of DNB to lighting changes.
Abstract. The aim of this study is to investigate the shallow thermal field differences for two differently aged passive continental margins by analyzing regional variations in geothermal gradient and exploring the controlling factors for these variations. Hence, we analyzed two previously published 3-D conductive and lithospheric-scale thermal models of the Southwest African and the Norwegian passive margins. These 3-D models differentiate various sedimentary, crustal, and mantle units and integrate different geophysical data such as seismic observations and the gravity field. We extracted the temperature–depth distributions in 1 km intervals down to 6 km below the upper thermal boundary condition. The geothermal gradient was then calculated for these intervals between the upper thermal boundary condition and the respective depth levels (1, 2, 3, 4, 5, and 6 km below the upper thermal boundary condition). According to our results, the geothermal gradient decreases with increasing depth and shows varying lateral trends and values for these two different margins. We compare the 3-D geological structural models and the geothermal gradient variations for both thermal models and show how radiogenic heat production, sediment insulating effect, and thermal lithosphere–asthenosphere boundary (LAB) depth influence the shallow thermal field pattern. The results indicate an ongoing process of oceanic mantle cooling at the young Norwegian margin compared with the old SW African passive margin that seems to be thermally equilibrated in the present day.
The aim of this study is to investigate the shal-
low thermal field differences for two differently aged pas-
sive continental margins by analyzing regional variations in
geothermal gradient and exploring the controlling factors for
these variations. Hence, we analyzed two previously pub-
lished 3-D conductive and lithospheric-scale thermal models
of the Southwest African and the Norwegian passive mar-
gins. These 3-D models differentiate various sedimentary,
crustal, and mantle units and integrate different geophysi-
cal data such as seismic observations and the gravity field.
We extracted the temperature–depth distributions in 1 km
intervals down to 6 km below the upper thermal boundary
condition. The geothermal gradient was then calculated for
these intervals between the upper thermal boundary condi-
tion and the respective depth levels (1, 2, 3, 4, 5, and 6 km
below the upper thermal boundary condition). According to
our results, the geothermal gradient decreases with increas-
ing depth and shows varying lateral trends and values for
these two different margins. We compare the 3-D geologi-
cal structural models and the geothermal gradient variations
for both thermal models and show how radiogenic heat pro-
duction, sediment insulating effect, and thermal lithosphere–
asthenosphere boundary (LAB) depth influence the shallow
thermal field pattern. The results indicate an ongoing process
of oceanic mantle cooling at the young Norwegian margin
compared with the old SW African passive margin that seems
to be thermally equilibrated in the present day.
Utilization of sunlight for energy harvesting has been foreseen as sustainable replacement for fossil fuels, which would also eliminate side effects arising from fossil fuel consumption such as drastic increase of CO2 in Earth atmosphere. Semiconductor materials can be implemented for energy harvesting, and design of ideal energy harvesting devices relies on effective semiconductor with low recombination rate, ease of processing, stability over long period, non-toxicity and synthesis from abundant sources. Aforementioned criteria have attracted broad interest for graphitic carbon nitride (g-CN) materials, metal-free semiconductor which can be synthesized from low cost and abundant precursors. Furthermore, physical properties such as band gap, surface area and absorption can be tuned. g-CN was investigated as heterogeneous catalyst, with diversified applications from water splitting to CO2 reduction and organic coupling reactions. However, low dispersibility of g-CN in water and organic solvents was an obstacle for future improvements.
Tissue engineering aims to mimic natural tissues mechanically and biologically, so that synthetic materials can replace natural ones in future. Hydrogels are crosslinked networks with high water content, therefore are prime candidates for tissue engineering. However, the first requirement is synthesis of hydrogels with mechanical properties that are matching to natural tissues. Among different approaches for reinforcement, nanocomposite reinforcement is highly promising.
This thesis aims to investigate aqueous and organic dispersions of g-CN materials. Aqueous g-CN dispersions were utilized for visible light induced hydrogel synthesis, where g-CN acts as reinforcer and photoinitiator. Varieties of methodologies were presented for enhancing g-CN dispersibility, from co-solvent method to prepolymer formation, and it was shown that hydrogels with diversified mechanical properties (from skin-like to cartilage-like) are accessible via g-CN utilization. One pot photografting method was introduced for functionalization of g-CN surface which provides functional groups towards enhanced dispersibility in aqueous and organic media. Grafting vinyl thiazole groups yields stable additive-free organodispersions of g-CN which are electrostatically stabilized with increased photophysical properties. Colloidal stability of organic systems provides transparent g-CN coatings and printing g-CN from commercial inkjet printers.
Overall, application of g-CN in dispersed media is highly promising, and variety of materials can be accessible via utilization of g-CN and visible light with simple chemicals and synthetic conditions. g-CN in dispersed media will bridge emerging research areas from tissue engineering to energy harvesting in near future.
Salt marshes filter pollutants, protect coastlines against storm surges, and sequester carbon, yet are under threat from sea level rise and anthropogenic modification. The sustained existence of the salt marsh ecosystem depends on the topographic evolution of marsh platforms. Quantifying marsh platform topography is vital for improving the management of these valuable landscapes. The determination of platform boundaries currently relies on supervised classification methods requiring near-infrared data to detect vegetation, or demands labour-intensive field surveys and digitisation. We propose a novel, unsupervised method to reproducibly isolate salt marsh scarps and platforms from a digital elevation model (DEM), referred to as Topographic Identification of Platforms (TIP). Field observations and numerical models show that salt marshes mature into subhorizontal platforms delineated by subvertical scarps. Based on this premise, we identify scarps as lines of local maxima on a slope raster, then fill landmasses from the scarps upward, thus isolating mature marsh platforms. We test the TIP method using lidar-derived DEMs from six salt marshes in England with varying tidal ranges and geometries, for which topographic platforms were manually isolated from tidal flats. Agreement between manual and unsupervised classification exceeds 94% for DEM resolutions of 1 m, with all but one site maintaining an accuracy superior to 90% for resolutions up to 3 m. For resolutions of 1 m, platforms detected with the TIP method are comparable in surface area to digitised platforms and have similar elevation distributions. We also find that our method allows for the accurate detection of local block failures as small as 3 times the DEM resolution. Detailed inspection reveals that although tidal creeks were digitised as part of the marsh platform, unsupervised classification categorises them as part of the tidal flat, causing an increase in false negatives and overall platform perimeter. This suggests our method may benefit from combination with existing creek detection algorithms. Fallen blocks and high tidal flat portions, associated with potential pioneer zones, can also lead to differences between our method and supervised mapping. Although pioneer zones prove difficult to classify using a topographic method, we suggest that these transition areas should be considered when analysing erosion and accretion processes, particularly in the case of incipient marsh platforms. Ultimately, we have shown that unsupervised classification of marsh platforms from high-resolution topography is possible and sufficient to monitor and analyse topographic evolution.
The climate is a complex dynamical system involving interactions and feedbacks among different processes at multiple temporal and spatial scales. Although numerous studies have attempted to understand the climate system, nonetheless, the studies investigating the multiscale characteristics of the climate are scarce. Further, the present set of techniques are limited in their ability to unravel the multi-scale variability of the climate system. It is completely plausible that extreme events and abrupt transitions, which are of great interest to climate community, are resultant of interactions among processes operating at multi-scale. For instance, storms, weather patterns, seasonal irregularities such as El Niño, floods and droughts, and decades-long climate variations can be better understood and even predicted by quantifying their multi-scale dynamics. This makes a strong argument to unravel the interaction and patterns of climatic processes at different scales. With this background, the thesis aims at developing measures to understand and quantify multi-scale interactions within the climate system.
In the first part of the thesis, I proposed two new methods, viz, multi-scale event synchronization (MSES) and wavelet multi-scale correlation (WMC) to capture the scale-specific features present in the climatic processes. The proposed methods were tested on various synthetic and real-world time series in order to check their applicability and replicability. The results indicate that both methods (WMC and MSES) are able to capture scale-specific associations that exist between processes at different time scales in a more detailed manner as compared to the traditional single scale counterparts.
In the second part of the thesis, the proposed multi-scale similarity measures were used in constructing climate networks to investigate the evolution of spatial connections within climatic processes at multiple timescales. The proposed methods WMC and MSES, together with complex network were applied to two different datasets.
In the first application, climate networks based on WMC were constructed for the univariate global sea surface temperature (SST) data to identify and visualize the SSTs patterns that develop very similarly over time and distinguish them from those that have long-range teleconnections to other ocean regions. Further investigations of climate networks on different timescales revealed (i) various high variability and co-variability regions, and (ii) short and long-range teleconnection regions with varying spatial distance. The outcomes of the study not only re-confirmed the existing knowledge on the link between SST patterns like El Niño Southern Oscillation and the Pacific Decadal Oscillation, but also suggested new insights into the characteristics and origins of long-range teleconnections.
In the second application, I used the developed non-linear MSES similarity measure to quantify the multivariate teleconnections between extreme Indian precipitation and climatic patterns with the highest relevance for Indian sub-continent. The results confirmed significant non-linear influences that were not well captured by the traditional methods. Further, there was a substantial variation in the strength and nature of teleconnection across India, and across time scales.
Overall, the results from investigations conducted in the thesis strongly highlight the need for considering the multi-scale aspects in climatic processes, and the proposed methods provide robust framework for quantifying the multi-scale characteristics.
The sequencing of the human genome in the early 2000s led to an increased interest in cheap and fast sequencing technologies. This interest culminated in the advent of next generation sequencing (NGS). A number of different NGS platforms have arisen since then all promising to do the same thing, i.e. produce large amounts of genetic information for relatively low costs compared to more traditional methods such as Sanger sequencing. The capabilities of NGS meant that researchers were no longer bound to species for which a lot of previous work had already been done (e.g. model organisms and humans) enabling a shift in research towards more novel and diverse species of interest. This capability has greatly benefitted many fields within the biological sciences, one of which being the field of evolutionary biology. Researchers have begun to move away from the study of laboratory model organisms to wild, natural populations and species which has greatly expanded our knowledge of evolution. NGS boasts a number of benefits over more traditional sequencing approaches. The main benefit comes from the capability to generate information for drastically more loci for a fraction of the cost. This is hugely beneficial to the study of wild animals as, even when large numbers of individuals are unobtainable, the amount of data produced still allows for accurate, reliable population and species level results from a small selection of individuals.
The use of NGS to study species for which little to no previous research has been carried out on and the production of novel evolutionary information and reference datasets for the greater scientific community were the focuses of this thesis. Two studies in this thesis focused on producing novel mitochondrial genomes from shotgun sequencing data through iterative mapping, bypassing the need for a close relative to serve as a reference sequence. These mitochondrial genomes were then used to infer species level relationships through phylogenetic analyses. The first of these studies involved reconstructing a complete mitochondrial genome of the bat eared fox (Otocyon megalotis). Phylogenetic analyses of the mitochondrial genome confidently placed the bat eared fox as sister to the clade consisting of the raccoon dog and true foxes within the canidae family. The next study also involved reconstructing a mitochondrial genome but in this case from the extinct Macrauchenia of South America. As this study utilised ancient DNA, it involved a lot of parameter testing, quality controls and strict thresholds to obtain a near complete mitochondrial genome devoid of contamination known to plague ancient DNA studies. Phylogenetic analyses confidently placed Macrauchenia as sister to all living representatives of Perissodactyla with a divergence time of ~66 million years ago. The third and final study of this thesis involved de novo assemblies of both nuclear and mitochondrial genomes from brown and striped hyena and focussed on demographic, genetic diversity and population genomic analyses within the brown hyena. Previous studies of the brown hyena hinted at very low levels of genomic diversity and, perhaps due to this, were unable to find any notable population structure across its range. By incorporating a large number of genetic loci, in the form of complete nuclear genomes, population structure within the brown hyena was uncovered. On top of this, genomic diversity levels were compared to a number of other species. Results showed the brown hyena to have the lowest genomic diversity out of all species included in the study which was perhaps caused by a continuous and ongoing decline in effective population size that started about one million years ago and dramatically accelerated towards the end of the Pleistocene.
The studies within this thesis show the power NGS sequencing has and its utility within evolutionary biology. The most notable capabilities outlined in this thesis involve the study of species for which no reference data is available and in the production of large amounts of data, providing evolutionary answers at the species and population level that data produced using more traditional techniques simply could not.
Since 2015, the European Union has struggled to deal with the influx of refugees coming into its territories. The number of institutions involved in designing a competent response approach, com-bined with the unilateral and uncoordinated state reactions, have left unclear where to look for when searching for answers and new alternatives. Can the United Nations High Commissioner for Refugees (UNHCR) take a leading role in solving this and future crises? After a brief recapitulation of the crisis, an analysis of UNHCR’s statue, relationship to international law, and doctrine will put this question to the test while exploring options that are not only available but also feasible in a system where politics trump both legality and morality. If UNHCR is to play an active role in fu-ture refugee policies and become the lead agency it once was, a new daring and innovative approach has to emerge in order to readapt to the power relations that prevail in the twenty-first century.
Plants are unable to move away from unwanted environments and therefore have to locally adapt to changing conditions. Arabidopsis thaliana (Arabidopsis), a model organism in plant biology, has been able to rapidly colonize a wide spectrum of environments with different biotic and abiotic challenges. In recent years, natural variation in Arabidopsis has shown to be an excellent resource to study genes underlying adaptive traits and hybridization’s impact on natural diversity. Studies on Arabidopsis hybrids have provided information on the genetic basis of hybrid incompatibilities and heterosis, as well as inheritance patterns in hybrids. However, previous studies have focused mainly on global accessions and yet much remains to be known about variation happening within a local growth habitat. In my PhD, I investigated the impact of heterozygosity at a local collection site of Arabidopsis and its role in local adaptation. I focused on two different projects, both including hybrids among Arabidopsis individuals collected around Tübingen in Southern Germany. The first project sought to understand the impact of hybridization on metabolism and growth within a local Arabidopsis collection site. For this, the inheritance patterns in primary and secondary metabolism, together with rosette size of full diallel crosses among seven parents originating from Southern Germany were analyzed. In comparison to primary metabolites, compounds from secondary metabolism were more variable and showed pronounced non-additive inheritance patterns. In addition, defense metabolites, mainly glucosinolates, displayed the highest degree of variation from the midparent values and were positively correlated with a proxy for plant size.
In the second project, the role of ACCELERATED CELL DEATH 6 (ACD6) in the defense response pathway of Arabidopsis necrotic hybrids was further characterized. Allelic interactions of ACD6 have been previously linked to hybrid necrosis, both among global and local Arabidopsis accessions. Hence, I characterized the early metabolic and ionic changes induced by ACD6, together with marker gene expression assays of physiological responses linked to its activation. An upregulation of simple sugars and metabolites linked to non-enzymatic antioxidants and the TCA cycle were detected, together with putrescine and acids linked to abiotic stress responses. Senescence was found to be induced earlier in necrotic hybrids and cytoplasmic calcium signaling was unaffected in response to temperature. In parallel, GFP-tagged constructs of ACD6 were developed.
This work therefore gave novel insights on the role of heterozygosity in natural variation and adaptation and expanded our current knowledge on the physiological and molecular responses associated with ACD6 activation.
The movement of organisms has formed our planet like few other processes. Movements shape populations, communities, entire ecosystems, and guarantee fundamental ecosystem functions and services, like seed dispersal and pollination. Global, regional and local anthropogenic impacts influence animal movements across ecosystems all around the world. In particular, land-use modification, like habitat loss and fragmentation disrupt movements between habitats with profound consequences, from increased disease transmissions to reduced species richness and abundance. However, neither the influence of anthropogenic change on animal movement processes nor the resulting effects on ecosystems are well understood. Therefore, we need a coherent understanding of organismal movement processes and their underlying mechanisms to predict and prevent altered animal movements and their consequences for ecosystem functions.
In this thesis I aim at understanding the influence of anthropogenically caused land-use change on animal movement processes and their underlying mechanisms. In particular, I am interested in the synergistic influence of large-scale landscape structure and fine-scale habitat features on basic-level movement behaviours (e.g. the daily amount of time spend running, foraging, and resting) and their emerging higher-level movements (home range formation). Based on my findings, I identify the likely consequences of altered animal movements that lead to the loss of species richness and abundances.
The study system of my thesis are hares in agricultural landscapes. European brown hares (Lepus europaeus) are perfectly suited to study animal movements in agricultural landscapes, as hares are hermerophiles and prefer open habitats. They have historically thrived in agricultural landscapes, but their numbers are in decline. Agricultural areas are undergoing strong land-use changes due to increasing food demand and fast developing agricultural technologies. They are already the largest land-use class, covering 38% of the world’s terrestrial surface. To consider the relevance of a given landscape structure for animal movement behaviour I selected two differently structured agricultural landscapes – a simple landscape in Northern Germany with large fields and few landscape elements (e.g. hedges and tree stands), and a complex landscape in Southern Germany with small fields and many landscape elements.
I applied GPS devices (hourly fixes) with internal high-resolution accelerometers (4 min samples) to track hares, receiving an almost continuous observation of the animals’ behaviours via acceleration analyses. I used the spatial and behavioural information in combination with remote sensing data (normalized difference vegetation index, or NDVI, a proxy for resource availability), generating an almost complete idea of what the animal was doing when, why and where. Apart from landscape structure (represented by the two differently structured study areas), I specifically tested whether the following fine-scale habitat features influence animal movements: resource, agricultural management events, habitat diversity, and habitat structure.
My results show that, irrespective of the movement process or mechanism and the type of fine-scale habitat features, landscape structure was the overarching variable influencing hare movement behaviour. High resource variability forces hares to enlarge their home ranges, but only in the simple and not in the complex landscape. Agricultural management events result in home range shifts in both landscapes, but force hares to increase their home ranges only in the simple landscape. Also the preference of habitat patches with low vegetation and the avoidance of high vegetation, was stronger in the simple landscape. High and dense crop fields restricted hare movements temporarily to very local and small habitat patch remnants. Such insuperable barriers can separate habitat patches that were previously connected by mobile links. Hence, the transport of nutrients and genetic material is temporarily disrupted. This mechanism is also working on a global scale, as human induced changes from habitat loss and fragmentation to expanding monocultures cause a reduction in animal movements worldwide.
The mechanisms behind those findings show that higher-level movements, like increasing home ranges, emerge from underlying basic-level movements, like the behavioural modes. An increasing landscape simplicity first acts on the behavioural modes, i.e. hares run and forage more, but have less time to rest. Hence, the emergence of increased home range sizes in simple landscapes is based on an increased proportion of time running and foraging, largely due to longer travelling times between distant habitats and scarce resource items in the landscape. This relationship was especially strong during the reproductive phase, demonstrating the importance of high-quality habitat for reproduction and the need to keep up self-maintenance first, in low quality areas. These changes in movement behaviour may release a cascade of processes that start with more time being allocated to running and foraging, resulting into an increased energy expenditure and may lead to a decline in individual fitness. A decrease in individual fitness and reproductive output will ultimately affect population viability leading to local extinctions.
In conclusion, I show that landscape structure has one of the most important effects on hare movement behaviour. Synergistic effects of landscape structure, and fine-scale habitat features, first affect and modify basic-level movement behaviours, that can scales up to altered higher-level movements and may even lead to the decline of species richness and abundances, and the disruption of ecosystem functions. Understanding the connection between movement mechanisms and processes can help to predict and prevent anthropogenically induced changes in movement behaviour. With regard to the paramount importance of landscape structure, I strongly recommend to decrease the size of agricultural fields and increase crop diversity. On the small-scale, conservation policies should assure the year round provision of areas with low vegetation height and high quality forage. This could be done by generating wildflower strips and additional (semi-) natural habitat patches. This will not only help to increase the populations of European brown hares and other farmland species, but also ensure and protects the continuity of mobile links and their intrinsic value for sustaining important ecosystem functions and services.
In this dissertation the lattice and the magnetic recovery dynamics of the two heavy rare-earth metals Dy and Gd after femtosecond photoexcitation are described. For the investigations, thin films of Dy and Gd were measured at low temperatures in the antiferromagnetic phase of Dy and close to room temperature in the ferromagnetic phase of Gd. Two different optical pump-x-ray probe techniques were employed: Ultrafast x-ray diffraction with hard x-rays (UXRD) yields the structural response of heavy rare-earth metals and resonant soft (elastic) x-ray diffraction (RSXD), which allows measuring directly changes in the helical antiferromagnetic order of Dy. The combination of both techniques enables to study the complex interaction between the magnetic and the phononic subsystems.
This publication based thesis, which consists of seven published articles, summarizes my contributions to the research field of laser excited ultrafast structural dynamics. The coherent and incoherent lattice dynamics on microscopic length scales are detected by ultrashort optical and X-ray pulses. The understanding of the complex physical processes is essential for future improvements of technological applications. For this purpose, tabletop soruces and large scale facilities, e.g. synchrotrons, are employed to study structural dynamics of longitudinal acoustic strain waves and heat transport. The investigated effects cover timescales from hundreds of femtoseconds up to several microseconds.
The main part of this thesis is dedicated to the investigation of tailored phonon wave packets propagating in perovskite nanostructures. Tailoring is achieved either by laser excitation of nanostructured bilayer samples or by a temporal series of laser pulses. Due to the propagation of longitudinal acoustic phonons, the out-of-plane lattice spacing of a thin film insulator-metal bilayer sample is modulated on an ultrafast timescale. This leads to an ultrafast modulation of the X-ray diffraction efficiency which is employed as a phonon Bragg switch to shorten hard X-ray pulses emitted from a 3rd generation synchrotron.
In addition, we have observed nonlinear mixing of high amplitude phonon wave packets which originates from an anharmonic interatomic potential. A chirped optical pulse sequence excites a narrow band phonon wave packet with specific momentum and energy. The second harmonic generation of these phonon wave packets is followed by ultrafast X-ray diffraction. Phonon upconversion takes place because the high amplitude phonon wave packet modulates the acoustic properties of the crystal which leads to self steepening and to the successive generation of higher harmonics of the phonon wave packet.
Furthermore, we have demonstrated ultrafast strain in direction parallel to the sample surface. Two consecutive so-called transient grating excitations displaced in space and time are used to coherently control thermal gradients and surface acoustic modes. The amplitude of the coherent and incoherent surface excursion is disentangled by time resolved X-ray reflectivity measurements. We calibrate the absolute amplitude of thermal and acoustic surface excursion with measurements of longitudinal phonon propagation. In addition, we develop a diffraction model which allows for measuring the surface excursion on an absolute length scale with sub-Äangström precision. Finally, I demonstrate full coherent control of an excited surface deformation by amplifying and suppressing thermal and coherent excitations at the surface of a laser-excited Yttrium-manganite sample.
Es gibt in Berlin eine einzigartige Vereinslandschaft im Amateur – und semiprofessionellen Fußballsport, in der einst von türkischen Migranten gegründete Vereine einen festen Platz einnehmen. Fußballsport bietet einen sozialen Raum für Jugendliche verschiedener kultureller, ethnischer und religiöser Herkunft, in dem Gruppen gebildet werden, um gegen einander zu konkurrieren. Ebenso eröffnet Fußball dem Einzelnen die Möglichkeit, die Gültigkeit und Relevanz von Vorurteilen und von gängigen Stereotypisierungen anderer Gruppen im Spielalltag einer ständigen Prüfung zu unterziehen. Fußballspieler können sich sowohl zwischen multi-kulturellen als auch mono-ethnischen Gruppenkonstellationen, in einigen Fällen auch in transnationalen Konstellationen bewegen, womit sie dabei wesentlich an der Sinngebung ihrer eigenen sozialen Zugehörigkeit mitwirken, die sich aus dem Spannungsfeld von Selbst- und Fremdwahrnehmungsmustern ergibt. In Folge dessen werden in diesem Raum Anerkennungsmechanismen konstituiert.
Die vorliegende Dissertation befasst sich mit dem alltäglichen Leben von türkisch-stämmigen, jugendlichen Amateur- und semiprofessionellen Fußballspielern (delikanli), sowie von anderen sozialen Akteuren der türkischen Fußballwelt, wie zum Beispiel „ältere“ Fußballspieler (agbi) und Fußballtrainer (hoca). Hauptanliegen der Arbeit war die Rekonstruktion kollektiver Wahrnehmungs-, Deutungs - und Handlungsmuster von Mitgliedern türkischer Fußballvereine im allgemeinen und ihrer Selbstdarstellung aber auch ihrer Wahrnehmung der „Anderen“ im besonderen. Mittels dieser Studie sollte nachvollzogen werden, ob und inwiefern sich traditionelle soziale Verhaltensmuster der gewählten Gruppe im technisch regulierten und stark Konkurrenz-orientierten Handlungsraum widerspiegeln und die reziproken Beziehungen zwischen dem „Selbst“ und den „Anderen“ regulieren. Dabei wurde die Relevanz von herkunftsbezogenen Stereotypisierungen und Vorurteilen in der kollektiven Konstitution von Selbstwahrnehmungen und Fremdverstehen im partikularen sozialen Feld (Bourdieu, 2001) des Fußballs rekonstruiert.
In dieser Arbeit wurde darüber hinaus beleuchtet, welche Rolle türkische Fußballvereine auf der einen Seite bei der Entstehung sozialer Raumzugehörigkeit zu den Stadtquartieren in Berlin einnehmen und welche Art von Mechanismen der sozialen Integration sie in diesen Vereinen herstellen. Auf der anderen Seite wurde hinterfragt, inwiefern sie zur sozialen Kohäsion zwischen diversen Kulturen beitragen. Daher wurde geprüft, ob und inwiefern die negativ konnotierte ethnozentrische Wahrnehmung von „Differenz“ (Bielefeld, 1998), die als soziales Konstrukt zwischen autochthonen und allochthonen Gruppen hergestellt wird, durch das Engagement der Vereinsakteure einen konstruktiven Wandel erfährt.
Übergeordnetes Ziel all dieser Forschungsfragen war es, ein fundiertes Verständnis über die Rolle von türkischen Fußballvereinen als soziale Mechanismen zu erlangen und deren Funktionsweise bei der Konstitution von Anpassungsstrategien in diesem sozialen Feld untersuchen. Detailliert wurde diese Rolle unter der Konzeptualisierung von sozialen Positionierungsmuster betrachtet, die als Gefüge von Deutungen des Alltäglichen verstanden werden, das individuelle und kollektive Handlungsmuster und implizit Muster des Fremdverstehens sowie des othering im Migrationskontext reguliert. Eine Rekonstruktion der sozialen Positionierungsmuster bietet eine eingehende soziologische Untersuchung dieser Teilnehmergruppe, die zudem Aufschluss über die Bedeutung und das Verständnis von ethnischer Zugehörigkeit für letztere gibt.
Neben umfangreicher Feldbeobachtung wurden in dieser qualitativen Studie mit Spielern verschiedener Vereine insgesamt zehn Gruppendiskussionen (Bohnsack, 2004) innerhalb ihrer Mannschaften zu gemeinsamen alltäglichen Erlebnissen und Erfahrungen durchgeführt, aufgezeichnet und mittels sozialwissenschaftlichem hermeneutischem Verfahren (Soeffner, 2004) interpretiert. Auch mit anderen Vereinsmitgliedern, d. h. mit Trainern bzw. hoca, Vorsitzenden, Managern und Sponsoren wurden jeweils zehn narrative und sieben biographische Einzelinterviews sowie sieben Experteninterviews durchgeführt. Deren Analyse erlaubt es, die Rolle dieser Mitglieder sowie wirkende Autoritätsmechanismen und kollektiv konstituierte Verhaltensmuster innerhalb der gesamten Vereinsgruppe zu rekonstruieren. Dabei wurde bezweckt, die Gesamtheit des sozialen Netzwerkes bzw. die Beziehungsschemata innerhalb der türkischen Fußballvereine Berlins zu verdeutlichen.
In der Arbeit werden zwei Standpunkte der theoretischen Auseinandersetzung verwendet. Auf der einen Seite wird die Lebensweltanalyse (Schütz und Luckmann, 1979, 1990) angewendet, um das soziale Erbe der in der Vergangenheit gesellschaftlich konstituierten Titulierung „Menschen mit Migrationshintergrund“ zu rekonstruieren, bzw. den Einfluss dieser sozialen Reproduktion auf die Wahrnehmungs-, Deutungs- und Handlungsmuster der Akteure zu untersuchen. Auf der anderen Seite wird die soziale Wirkung der tatsächlichen, alltäglichen Erfahrungsschemata im sozialen Feld des Fußballs auf die Selbstpositionierungen der Akteure mittels Goffmanscher Rahmenanalyse (Goffman, 1980) herausgearbeitet.
Arctic tundra landscapes are composed of a complex mosaic of patterned ground features, varying in soil moisture, vegetation composition, and surface hydrology over small spatial scales (10-100 m). The importance of microtopography and associated geomorphic landforms in influencing ecosystem structure and function is well founded, however, spatial data products describing local to regional scale distribution of patterned ground or polygonal tundra geomorphology are largely unavailable. Thus, our understanding of local impacts on regional scale processes (e.g., carbon dynamics) may be limited. We produced two key spatiotemporal datasets spanning the Arctic Coastal Plain of northern Alaska (similar to 60,000 km(2)) to evaluate climate-geomorphological controls on arctic tundra productivity change, using (1) a novel 30m classification of polygonal tundra geomorphology and (2) decadal-trends in surface greenness using the Landsat archive (1999-2014). These datasets can be easily integrated and adapted in an array of local to regional applications such as (1) upscaling plot-level measurements (e.g., carbon/energy fluxes), (2) mapping of soils, vegetation, or permafrost, and/or (3) initializing ecosystem biogeochemistry, hydrology, and/or habitat modeling.
Peatlands represent large terrestrial carbon banks. Given that most peat accumulates in boreal regions, where low temperatures and water saturation preserve organic matter, the existence of peat in (sub)tropical regions remains enigmatic. Here we examined peat and plant chemistry across a latitudinal transect from the Arctic to the tropics. Near-surface low-latitude peat has lower carbohydrate and greater aromatic content than near-surface high-latitude peat, creating a reduced oxidation state and resulting recalcitrance. This recalcitrance allows peat to persist in the (sub)tropics despite warm temperatures. Because we observed similar declines in carbohydrate content with depth in high-latitude peat, our data explain recent field-scale deep peat warming experiments in which catotelm (deeper) peat remained stable despite temperature increases up to 9 degrees C. We suggest that high-latitude deep peat reservoirs may be stabilized in the face of climate change by their ultimately lower carbohydrate and higher aromatic composition, similar to tropical peats.
Background: Individuals with aphasia after stroke (IWA) often present with working memory (WM) deficits. Research investigating the relationship between WM and language abilities has led to the promising hypothesis that treatments of WM could lead to improvements in language, a phenomenon known as transfer. Although recent treatment protocols have been successful in improving WM, the evidence to date is scarce and the extent to which improvements in trained tasks of WM transfer to untrained memory tasks, spoken sentence comprehension, and functional communication is yet poorly understood.
Aims: We aimed at (a) investigating whether WM can be improved through an adaptive n-back training in IWA (Study 1–3); (b) testing whether WM training leads to near transfer to unpracticed WM tasks (Study 1–3), and far transfer to spoken sentence comprehension (Study 1–3), functional communication (Study 2–3), and memory in daily life in IWA (Study 2–3); and (c) evaluating the methodological quality of existing WM treatments in IWA (Study 3). To address these goals, we conducted two empirical studies – a case-controls study with Hungarian speaking IWA (Study 1) and a multiple baseline study with German speaking IWA (Study 2) – and a systematic review (Study 3).
Methods: In Study 1 and 2 participants with chronic, post-stroke aphasia performed an adaptive, computerized n-back training. ‘Adaptivity’ was implemented by adjusting the tasks’ difficulty level according to the participants’ performance, ensuring that they always practiced at an optimal level of difficulty. To assess the specificity of transfer effects and to better understand the underlying mechanisms of transfer on spoken sentence comprehension, we included an outcome measure testing specific syntactic structures that have been proposed to involve WM processes (e.g., non-canonical structures with varying complexity).
Results: We detected a mixed pattern of training and transfer effects across individuals: five participants out of six significantly improved in the n-back training. Our most important finding is that all six participants improved significantly in spoken sentence comprehension (i.e., far transfer effects). In addition, we also found far transfer to functional communication (in two participants out of three in Study 2) and everyday memory functioning (in all three participants in Study 2), and near transfer to unpracticed n-back tasks (in four participants out of six). Pooled data analysis of Study 1 and 2 showed a significant negative relationship between initial spoken sentence comprehension and the amount of improvement in this ability, suggesting that the more severe the participants’ spoken sentence comprehension deficit was at the beginning of training, the more they improved after training. Taken together, we detected both near far and transfer effects in our studies, but the effects varied across participants. The systematic review evaluating the methodological quality of existing WM treatments in stroke IWA (Study 3) showed poor internal and external validity across the included 17 studies. Poor internal validity was mainly due to use of inappropriate design, lack of randomization of study phases, lack of blinding of participants and/or assessors, and insufficient sampling. Low external validity was mainly related to incomplete information on the setting, lack of use of appropriate analysis or justification for the suitability of the analysis procedure used, and lack of replication across participants and/or behaviors. Results in terms of WM, spoken sentence comprehension, and reading are promising, but further studies with more rigorous methodology and stronger experimental control are needed to determine the beneficial effects of WM intervention.
Conclusions: Results of the empirical studies suggest that WM can be improved with a computerized and adaptive WM training, and improvements can lead to transfer effects to spoken sentence comprehension and functional communication in some individuals with chronic post-stroke aphasia. The fact that improvements were not specific to certain syntactic structures (i.e., non-canonical complex sentences) in spoken sentence comprehension suggest that WM is not involved in the online, automatic processing of syntactic information (i.e., parsing and interpretation), but plays a more general role in the later stage of spoken sentence comprehension (i.e., post-interpretive comprehension). The individual differences in treatment outcomes call for future research to clarify how far these results are generalizable to the population level of IWA. Future studies are needed to identify a few mechanisms that may generalize to at least a subpopulation of IWA as well as to investigate baseline non-linguistic cognitive and language abilities that may play a role in transfer effects and the maintenance of such effects. These may require larger yet homogenous samples.
For more than two centuries, plant ecologists have aimed to understand how environmental gradients and biotic interactions shape the distribution and co-occurrence of plant species. In recent years, functional trait–based approaches have been increasingly used to predict patterns of species co-occurrence and species distributions along environmental gradients (trait–environment relationships). Functional traits are measurable properties at the individual level that correlate well with important processes. Thus, they allow us to identify general patterns by synthesizing studies across specific taxonomic compositions, thereby fostering our understanding of the underlying processes of species assembly. However, the importance of specific processes have been shown to be highly dependent on the spatial scale under consideration. In particular, it remains uncertain which mechanisms drive species assembly and allow for plant species coexistence at smaller, more local spatial scales. Furthermore, there is still no consensus on how particular environmental gradients affect the trait composition of plant communities. For example, increasing drought because of climate change is predicted to be a main threat to plant diversity, although it remains unclear which traits of species respond to increasing aridity. Similarly, there is conflicting evidence of how soil fertilization affects the traits related to establishment ability (e.g., seed mass). In this cumulative dissertation, I present three empirical trait-based studies that investigate specific research questions in order to improve our understanding of species distributions along environmental gradients.
In the first case study, I analyze how annual species assemble at the local scale and how environmental heterogeneity affects different facets of biodiversity—i.e. taxonomic, functional, and phylogenetic diversity—at different spatial scales. The study was conducted in a semi-arid environment at the transition zone between desert and Mediterranean ecosystems that features a sharp precipitation gradient (Israel). Different null model analyses revealed strong support for environmentally driven species assembly at the local scale, since species with similar traits tended to co-occur and shared high abundances within microsites (trait convergence). A phylogenetic approach, which assumes that closely related species are functionally more similar to each other than distantly related ones, partly supported these results. However, I observed that species abundances within microsites were, surprisingly, more evenly distributed across the phylogenetic tree than expected (phylogenetic overdispersion). Furthermore, I showed that environmental heterogeneity has a positive effect on diversity, which was higher on functional than on taxonomic diversity and increased with spatial scale. The results of this case study indicate that environmental heterogeneity may act as a stabilizing factor to maintain species diversity at local scales, since it influenced species distribution according to their traits and positively influenced diversity. All results were constant along the precipitation gradient.
In the second case study (same study system as case study one), I explore the trait responses of two Mediterranean annuals (Geropogon hybridus and Crupina crupinastrum) along a precipitation gradient that is comparable to the maximum changes in precipitation predicted to occur by the end of this century (i.e., −30%). The heterocarpic G. hybridus showed strong trends in seed traits, suggesting that dispersal ability increased with aridity. By contrast, the homocarpic C. crupinastrum showed only a decrease in plant height as aridity increased, while leaf traits of both species showed no consistent pattern along the precipitation gradient. Furthermore, variance decomposition of traits revealed that most of the trait variation observed in the study system was actually found within populations. I conclude that trait responses towards aridity are highly species-specific and that the amount of precipitation is not the most striking environmental factor at this particular scale.
In the third case study, I assess how soil fertilization mediates—directly by increased nutrient addition and indirectly by increased competition—the effect of seed mass on establishment ability. For this experiment, I used 22 species differing in seed mass from dry grasslands in northeastern Germany and analyzed the interacting effects of seed mass with nutrient availability and competition on four key components of seedling establishment: seedling emergence, time of seedling emergence, seedling survival, and seedling growth. (Time of) seedling emergence was not affected by seed mass. However, I observed that the positive effect of seed mass on seedling survival is lowered under conditions of high nutrient availability, whereas the positive effect of seed mass on seedling growth was only reduced by competition. Based on these findings, I developed a conceptual model of how seed mass should change along a soil fertility gradient in order to reconcile conflicting findings from the literature. In this model, seed mass shows a U-shaped pattern along the soil fertility gradient as a result of changing nutrient availability and competition.
Overall, the three case studies highlight the role of environmental factors on species distribution and co-occurrence. Moreover, the findings of this thesis indicate that spatial heterogeneity at local scales may act as a stabilizing factor that allows species with different traits to coexist. In the concluding discussion, I critically debate intraspecific trait variability in plant community ecology, the use of phylogenetic relationships and easily measured key functional traits as a proxy for species’ niches. Finally, I offer my outlook for the future of functional plant community research.
Version control is a widely used practice among software developers. It reduces the risk of changing their software and allows them to manage different configurations and to collaborate with others more efficiently. This is amplified by code sharing platforms such as GitHub or Bitbucket. Most version control systems track files (e.g., Git, Mercurial, and Subversion do), but some programming environments do not operate on files, but on objects instead (many Smalltalk implementations do). Users of such environments want to use version control for their objects anyway. Specialized version control systems, such as the ones available for Smalltalk systems (e.g., ENVY/Developer and Monticello), focus on a small subset of objects that can be versioned. Most of these systems concentrate on the tracking of methods, classes, and configurations of these. Other user-defined and user-built objects are either not eligible for version control at all, tracking them involves complicated workarounds, or a fixed, domain-unspecific serialization format is used that does not equally suit all kinds of objects. Moreover, these version control systems that are specific to a programming environment require their own code sharing platforms; popular, well-established platforms for file-based version control systems cannot be used or adapter solutions need to be implemented and maintained.
To improve the situation for version control of arbitrary objects, a framework for tracking, converting, and storing of objects is presented in this report. It allows editions of objects to be stored in an exchangeable, existing backend version control system. The platforms of the backend version control system can thus be reused. Users and objects have control over how objects are captured for the purpose of version control. Domain-specific requirements can be implemented. The storage format (i.e. the file format, when file-based backend version control systems are used) can also vary from one object to another. Different editions of objects can be compared and sets of changes can be applied to graphs of objects. A generic way for capturing and restoring that supports most kinds of objects is described. It models each object as a collection of slots. Thus, users can begin to track their objects without first having to implement version control supplements for their own kinds of objects. The proposed architecture is evaluated using a prototype implementation that can be used to track objects in Squeak/Smalltalk with Git. The prototype improves the suboptimal standing of user objects with respect to version control described above and also simplifies some version control tasks for classes and methods as well. It also raises new problems, which are discussed in this report as well.
Flooding is an imminent natural hazard threatening most river deltas, e.g. the Mekong Delta. An appropriate flood management is thus required for a sustainable development of the often densely populated regions. Recently, the traditional event-based hazard control shifted towards a risk management approach in many regions, driven by intensive research leading to new legal regulation on flood management. However, a large-scale flood risk assessment does not exist for the Mekong Delta. Particularly, flood risk to paddy rice cultivation, the most important economic activity in the delta, has not been performed yet. Therefore, the present study was developed to provide the very first insight into delta-scale flood damages and risks to rice cultivation. The flood hazard was quantified by probabilistic flood hazard maps of the whole delta using a bivariate extreme value statistics, synthetic flood hydrographs, and a large-scale hydraulic model. The flood risk to paddy rice was then quantified considering cropping calendars, rice phenology, and harvest times based on a time series of enhanced vegetation index (EVI) derived from MODIS satellite data, and a published rice flood damage function. The proposed concept provided flood risk maps to paddy rice for the Mekong Delta in terms of expected annual damage. The presented concept can be used as a blueprint for regions facing similar problems due to its generic approach. Furthermore, the changes in flood risk to paddy rice caused by changes in land use currently under discussion in the Mekong Delta were estimated. Two land-use scenarios either intensifying or reducing rice cropping were considered, and the changes in risk were presented in spatially explicit flood risk maps. The basic risk maps could serve as guidance for the authorities to develop spatially explicit flood management and mitigation plans for the delta. The land-use change risk maps could further be used for adaptive risk management plans and as a basis for a cost-benefit of the discussed land-use change scenarios. Additionally, the damage and risks maps may support the recently initiated agricultural insurance programme in Vietnam.
Reversible-deactivation radical polymerization (RDRP) is without any doubt one of the most prevalent and powerful strategies for polymer synthesis, by which well-defined living polymers with targeted molecular weight (MW), low molar dispersity (Ɖ) and diverse morphologies can be prepared in a controlled fashion. Atom transfer radical polymerization (ATRP) as one of the most extensive studied types of RDRP has been particularly emphasized due to the high accessibility to hybrid materials, multifunctional copolymers and diverse end group functionalities via commercially available precursors. However, due to catalyst-induced side reactions and chain-chain coupling termination in bulk environment, synthesis of high MW polymers with uniform chain length (low Ɖ) and highly-preserved chain-end fidelity is usually challenging. Besides, owing to the inherited radical nature, the control of microstructure, namely tacticity control, is another laborious task. Considering the applied catalysts, the utilization of large amounts of non-reusable transition metal ions which lead to cumbersome purification process, product contamination and complicated reaction procedures all delimit the scope ATRP techniques.
Metal-organic frameworks (MOFs) are an emerging type of porous materials combing the properties of both organic polymers and inorganic crystals, characterized with well-defined crystalline framework, high specific surface area, tunable porous structure and versatile nanochannel functionalities. These promising properties of MOFs have thoroughly revolutionized academic research and applications in tremendous aspects, including gas processing, sensing, photoluminescence, catalysis and compartmentalized polymerization. Through functionalization, the microenvironment of MOF nanochannel can be precisely devised and tailored with specified functional groups for individual host-guest interactions. Furthermore, properties of high transition metal density, accessible catalytic sites and crystalline particles all indicate MOFs as prominent heterogeneous catalysts which open a new avenue towards unprecedented catalytic performance. Although beneficial properties in catalysis, high agglomeration and poor dispersibility restrain the potential catalytic capacity to certain degree.
Due to thriving development of MOF sciences, fundamental polymer science is undergoing a significant transformation, and the advanced polymerization strategy can eventually refine the intrinsic drawbacks of MOF solids reversely. Therefore, in the present thesis, a combination of low-dimensional polymers with crystalline MOFs is demonstrated as a robust and comprehensive approach to gain the bilateral advantages from polymers (flexibility, dispersibility) and MOFs (stability, crystallinity). The utilization of MOFs for in-situ polymerizations and catalytic purposes can be realized to synthesize intriguing polymers in a facile and universal process to expand the applicability of conventional ATRP methodology. On the other hand, through the formation of MOF/polymer composites by surface functionalization, the MOF particles with environment-adjustable dispersibility and high catalytic property can be as-prepared.
In the present thesis, an approach via combination of confined porous textures from MOFs and controlled radical polymerization is proposed to advance synthetic polymer chemistry. Zn2(bdc)2(dabco) (Znbdc) and the initiator-functionalized Zn MOFs, ZnBrbdc, are utilized as a reaction environment for in-situ polymerization of various size-dependent methacrylate monomers (i.e. methyl, ethyl, benzyl and isobornyl methacrylate) through (surface-initiated) activators regenerated by electron transfer (ARGET/SI-ARGET) ATRP, resulting in polymers with control over dispersity, end functionalities and tacticity with respect to distinct molecular size. While the functionalized MOFs are applied, due to the strengthened compartmentalization effect, the accommodated polymers with molecular weight up to 392,000 can be achieved. Moreover, a significant improvement in end-group fidelity and stereocontrol can be observed. The results highlight a combination of MOFs and ATRP is a promising and universal methodology to synthesize versatile well-defined polymers with high molecular weight, increment in isotactic trial and the preserved chain-end functionality.
More than being a host only, MOFs can act as heterogeneous catalysts for metal-catalyzed polymerizations. A Cu(II)-based MOF, Cu2(bdc)2(dabco), is demonstrated as a heterogeneous, universal catalyst for both thermal or visible light-triggered ARGET ATRP with expanded monomer range. The accessible catalytic metal sites enable the Cu(II) MOF to polymerize various monomers, including benzyl methacrylate (BzMA), styrene, methyl methacrylate (MMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA) in the fashion of ARGET ATRP. Furthermore, due to the robust frameworks, surpassing the conventional homogeneous catalyst, the Cu(II) MOF can tolerate strongly coordinating monomers and polymerize challenging monomers (i.e. 4-vinyl pyridine, 2-vinyl pyridine and isoprene), in a well-controlled fashion. Therefore, a synthetic procedure can be significantly simplified, and catalyst-resulted chelation can be avoided as well. Like other heterogeneous catalysts, the Cu(II) MOF catalytic complexes can be easily collected by centrifugation and recycled for an arbitrary amount of times.
The Cu(II) MOF, composed of photostimulable metal sites, is further used to catalyze controlled photopolymerization under visible light and requires no external photoinitiator, dye sensitizer or ligand. A simple light trigger allows the photoreduction of Cu(II) to the active Cu(I) state, enabling controlled polymerization in the form of ARGET ATRP. More than polymerization application, the synergic effect between MOF frameworks and incorporated nucleophilic monomers/molecules is also observed, where the formation of associating complexes is able to adjust the photochemical and electrochemical properties of the Cu(II) MOF, altering the band gap and light harvesting behavior. Owing to the tunable photoabsorption property resulting from the coordinating guests, photoinduced Reversible-deactivation radical polymerization (PRDRP) can be achieved to further simplify and fasten the polymerization.
More than the adjustable photoabsorption ability, the synergistic strategy via a combination of controlled/living polymerization technique and crystalline MOFs can be again evidenced as demonstrated in the MOF-based heterogeneous catalysts with enhanced dispersibility in solution. Through introducing hollow pollen pivots with surface immobilized environment-responsive polymer, PDMAEMA, highly dispersed MOF nanocrystals can be prepared after associating on polymer brushes via the intrinsic amine functionality in each DMAEMA monomer. Intriguingly, the pollen-PDMAEMA composite can serve as a “smart” anchor to trap nanoMOF particles with improved dispersibility, and thus to significantly enhance liquid-phase photocatalytic performance. Furthermore, the catalytic activity can be switched on and off via stimulable coil-to-globule transition of the PDMAEMA chains exposing or burying MOF catalytic sites, respectively.
Three Essays on EFRAG
(2018)
This cumulative doctoral thesis consists of three papers that deal with the role of one specific European accounting player in the international accounting standard-setting, namely the European Financial Reporting Advisory Group (EFRAG). The first paper examines whether and how EFRAG generally fulfills its role in articulating Europe’s interests toward the International Accounting Standards Board (IASB). The qualitative data from the conducted interviews reveal that EFRAG influences the IASB’s decision making at a very early stage, long before other constituents are officially asked to comment on the IASB’s proposals. The second paper uses quantitative data and investigates the formal participation behavior of European constituents that seek to determine EFRAG’s voice. More precisely, this paper analyzes the nature of the constituents’ participation in EFRAG’s due process in terms of representation (constituent groups and geographical distribution) and the drivers of their participation behavior. EFRAG’s official decision making process is dominated by some specific constituent groups (such as preparers and the accounting profession) and by constituents from some specific countries (e.g. those with effective enforcement regimes). The third paper investigates in a first step who of the European constituents choose which lobbying channel (participation only at IASB, only at EFRAG, or at both institutions) and unveils in a second step possible reasons for their lobbying choices. The paper comprises quantitative and qualitative data. It reveals that English skills, time issues, the size of the constituent, and the country of origin are factors that can explain why the majority participates only in the IASB’s due process.
Thermoresponsive block copolymers of presumably highly biocompatible character exhibiting upper critical solution temperature (UCST) type phase behavior were developed. In particular, these polymers were designed to exhibit UCST-type cloud points (Tcp) in physiological saline solution (9 g/L) within the physiologically interesting window of 30-50°C. Further, their use as carrier for controlled release purposes was explored. Polyzwitterion-based block copolymers were synthesized by atom transfer radical polymerization (ATRP) via a macroinitiator approach with varied molar masses and co-monomer contents. These block copolymers can self-assemble in the amphiphilic state to form micelles, when the thermoresponsive block experiences a coil-to-globule transition upon cooling. Poly(ethylene glycol) methyl ether (mPEG) was used as the permanently hydrophilic block to stabilize the colloids formed, and polyzwitterions as the thermoresponsive block to promote the temperature-triggered assembly-disassembly of the micellear aggregates at low temperature.
Three zwitterionic monomers were used for this studies, namely 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (SPE), 4-((2-(methacryloyl- oxy)ethyl)dimethylammonio)butane-1-sulfonate (SBE), and 3-((2-(methacryloyloxy)ethyl)- dimethylammonio)propane-1-sulfate) (ZPE). Their (co)polymers were characterized with respect to their molecular structure by proton nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC). Their phase behaviors in pure water as well as in physiological saline were studied by turbidimetry and dynamic light scattering (DLS). These (co)polymers are thermoresponsive with UCST-type phase behavior in aqueous solution. Their phase transition temperatures depend strongly on the molar masses and the incorporation of co-monomers: phase transition temperatures increased with increasing molar masses and content of poorly water-soluble co-monomer. In addition, the presence of salt influenced the phase transition dramatically. The phase transition temperature decreased with increasing salt content in the solution. While the PSPE homopolymers show a phase transition only in pure water, the PZPE homopolymers are able to exhibit a phase transition only in high salinity, as in physiological saline. Although both polyzwitterions have similar chemical structures that differ only in the anionic group (sulfonate group in SPE and sulfate group in ZPE), the water solubility is very different. Therefore, the phase transition temperatures of targeted block copolymers were modulated by using statistical copolymer of SPE and ZPE as thermoresponsive block, and varying the ratio of SPE to ZPE. Indeed, the statistical copolymers of P(SPE-co-ZPE) show phase transitions both in pure water as well as in physiological saline. Surprisingly, it was found that mPEG-b-PSBE block copolymer can display “schizophrenic” behavior in pure water, with the UCST-type cloud point occurring at lower temperature than the LCST-type one.
The block copolymer, which satisfied best the boundary conditions, is block copolymer mPEG114-b-P(SPE43-co-ZPE39) with a cloud point of 45°C in physiological saline. Therefore, it was chosen for solubilization studies of several solvatochromic dyes as models of active agents, using the thermoresponsive block copolymer as “smart” carrier. The uptake and release of the dyes were explored by UV-Vis and fluorescence spectroscopy, following the shift of the wavelength of the absorbance or emission maxima at low and high temperature. These are representative for the loaded and released state, respectively. However, no UCST-transition triggered uptake and release of these dyes could be observed. Possibly, the poor affinity of the polybetaines to the dyes in aqueous environtments may be related to the widely reported antifouling properties of zwitterionic polymers.
The thermal structure of subduction zones exerts a major influence on deep-seated mechanical and chemical processes controlling arc magmatism, seismicity, and global element cycles. Accretionary complexes exposed inland may comprise tectonic blocks with contrasting pressure-temperature (P-T) histories, making it possible to investigate the dynamics and thermal evolution of former subduction interfaces. With this aim, we present new Lu-Hf geochronological results for mafic rocks of the Halilbagi Complex (Anatolia) that evolved along different thermal gradients. Samples include a lawsonite-epidote blueschist, a lawsonite-epidote eclogite, and an epidote eclogite (all with counter-clockwise P-T paths), a prograde lawsonite blueschist with a "hairpin"-type P-T path, and a garnet amphibolite from the overlying sub-ophiolitic metamorphic sole. Equilibrium phase diagrams suggest that the garnet amphibolite formed at similar to 0.6-0.7 GPa and 800-850 degrees C, whereas the prograde lawsonite blueschist records burial from 2.1 GPa and 420 degrees C to 2.6 GPa and 520 degrees C. Well-defined Lu-Hf isochrons were obtained for the epidote eclogite (92.38 +/- 0.22 Ma) and the lawsonite-epidote blueschist (90.19 +/- 0.54 Ma), suggesting rapid garnet growth. The lawsonite-epidote eclogite (87.30 +/- 0.39 Ma) and the prograde lawsonite blueschist (ca. 86 Ma) are younger, whereas the garnet amphibolite (104.5 +/- 3.5 Ma) is older. Our data reveal a consistent trend of progressively decreasing geothermal gradient from granulite-facies conditions at similar to 104 Ma to the epidote-eclogite facies around 92 Ma, and the lawsonite blueschist-facies between 90 Ma and 86 Ma. Three Lu-Hf garnet dates (between 92 Ma and 87 Ma) weighted toward the growth of post-peak rims (as indicated by Lu distribution in garnet) suggest that the HP/LT rocks were exhumed continuously and not episodically. We infer that HP/LT metamorphic rocks within the Halilbagi Complex were subjected to continuous return flow, with "warm" rocks being exhumed during the tectonic burial of "cold" ones. Our results, combined with regional geological constraints, allow us to speculate that subduction started at a transform fault near a mid-oceanic spreading centre. Following its formation, this ancient subduction interface evolved thermally over more than 15 Myr, most likely as a result of heat dissipation rather than crustal underplating.
It is a common finding across languages that young children have problems in understanding patient-initial sentences. We used Tagalog, a verb-initial language with a reliable voice-marking system and highly frequent patient voice constructions, to test the predictions of several accounts that have been proposed to explain this difficulty: the frequency account, the Competition Model, and the incremental processing account. Study 1 presents an analysis of Tagalog child-directed speech, which showed that the dominant argument order is agent-before-patient and that morphosyntactic markers are highly valid cues to thematic role assignment. In Study 2, we used a combined self-paced listening and picture verification task to test how Tagalog-speaking adults and 5- and 7-year-old children process reversible transitive sentences. Results showed that adults performed well in all conditions, while children's accuracy and listening times for the first noun phrase indicated more difficulty in interpreting patient-initial sentences in the agent voice compared to the patient voice. The patient voice advantage is partly explained by both the frequency account and incremental processing account.
Thematic role assignment and word order preferences in the child language acquisition of Tagalog
(2018)
A critical task in daily communications is identifying who did what to whom in an utterance, or assigning the thematic roles agent and patient in a sentence. This dissertation is concerned with Tagalog-speaking children’s use of word order and morphosyntactic markers for thematic role assignment. It aims to explain children’s difficulties in interpreting sentences with a non-canonical order of arguments (i.e., patient-before-agent) by testing the predictions of the following accounts: the frequency account (Demuth, 1989), the Competition model (MacWhinney & Bates, 1989), and the incremental processing account (Trueswell & Gleitman, 2004). Moreover, the experiments in this dissertation test the influence of a word order strategy in a language like Tagalog, where the thematic roles are always unambiguous in a sentence, due to its verb-initial order and its voice-marking system. In Tagalog’s voice-marking system, the inflection on the verb indicates the thematic role of the noun marked by 'ang.' First, the possible basis for a word order strategy in Tagalog was established using a sentence completion experiment given to adults and 5- and 7-year-old children (Chapter 2) and a child-directed speech corpus analysis (Chapter 3). In general, adults and children showed an agent-before-patient preference, although adults’ preference was also affected by sentence voice. Children’s comprehension was then examined through a self-paced listening and picture verification task (Chapter 3) and an eye-tracking and picture selection task (Chapter 4), where word order (agent-initial or patient-initial) and voice (agent voice or patient voice) were manipulated. Offline (i.e., accuracy) and online (i.e., listening times, looks to the target) measures revealed that 5- and 7-year-old Tagalog-speaking children had a bias to interpret the first noun as the agent. Additionally, the use of word order and morphosyntactic markers was found to be modulated by voice. In the agent voice, children relied more on a word order strategy; while in the patient voice, they relied on the morphosyntactic markers. These results are only partially explained by the accounts being tested in this dissertation. Instead, the findings support computational accounts of incremental word prediction and learning such as Chang, Dell, & Bock’s (2006) model.
The use of functional music in gait training termed rhythmic auditory stimulation (RAS) and treadmill training (TT) have both been shown to be effective in stroke patients (SP). The combination of RAS and treadmill training (RAS-TT) has not been clinically evaluated to date. The aim of the study was to evaluate the efficacy of RAS-TT on functional gait in SR The protocol followed the design of an explorative study with a rater-blinded three arm prospective randomized controlled parallel group design. Forty-five independently walking SP with a hemiparesis of the lower limb or an unsafe and asymmetrical walking pattern were recruited. RAS-TT was carried out over 4 weeks with TT and neurodevelopmental treatment based on Bobath approach (NDT) serving as control interventions. For RAS-TT functional music was adjusted individually while walking on the treadmill. Pre and post-assessments consisted of the fast gait speed test (FGS), a gait analysis with the locometre (LOC), 3 min walking time test (3MWT), and an instrumental evaluation of balance (IEB). Raters were blinded to group assignments. An analysis of covariance (ANCOVA) was performed with affiliated measures from pre-assessment and time between stroke and start of study as covariates. Thirty-five participants (mean age 63.6 +/- 8.6 years, mean time between stroke and start of study 42.1 +/- 23.7 days) completed the study (11 RAS-TT, 13 TT, 11 NDT). Significant group differences occurred in the FGS for adjusted post-measures in gait velocity [F-(2,F- (34)) = 3.864, p = 0.032; partial eta(2) = 0.205] and cadence [F-(2,F- 34) = 7.656, p = 0.002; partial eta(2) = 0.338]. Group contrasts showed significantly higher values for RAS-TT. Stride length results did not vary between the groups. LOC, 3MWT, and IEB did not indicate group differences. One patient was withdrawn from TT because of pain in one arm. The study provides first evidence for a higher efficacy of RAS-TT in comparison to the standard approaches TT and NDT in restoring functional gait in SP. The results support the implementation of functional music in neurological gait rehabilitation and its use in combination with treadmill training.
The Timpa delle Murge ophiolite in the North Calabrian Unit is part of the Liguride Complex (southern Apennines). The study is concentrated on the gabbroic part of the ophiolite of the Pollino area. They preserve the high-grade ocean floor metamorphic and locally developed flaser textures under ocean floor conditions. The primary magmatic assemblages are clinopyroxene, plagioclase, and opaques. Brown hornblende is a late magmatic phase. Green hornblende, actinolite, albite, chlorite and epidote display metamorphic recrystallization under lower amphibolite facies conditions, followed by greenschist facies.
The gabbros show subalkaline near to alkaline character with a tendency to a more calkalkaline trend. The normalization to primitive mantle and mid-ocean ridge basalt (N-MORB) compositions indicates a considerable depletion in Nb, P, Zr and Ti and an enrichment in Ba, Rb, K, Sr and Eu. This points to a mantle source, which is not compatible with a "normal" mid-ocean ridge situation. Rather, the gabbros are generated from a N-MORB-like melt with a strong crustal component, which was influenced by subduction related fluids and episodic melting during mid-ocean-ridge processes.
Plausible geodynamic settings of the Timpa delle Murge gabbros are oceanic back-arc positions with embryonic MORB-activities. Similar slab contaminated magmatism is also known from the early stage of island arc formation in supra-subduction zone environments like the Izu-Bonin-Mariana island arc.
Specialized glial subtypes provide support to developing and functioning neural networks. Astrocytes modulate information processing by neurotransmitter recycling and release of neuromodulatory substances, whereas ensheathing glial cells have not been associated with neuromodulatory functions yet. To decipher a possible role of ensheathing glia in neuronal information processing, we screened for glial genes required in the Drosophila central nervous system for normal locomotor behavior. Shopper encodes a mitochondrial sulfite oxidase that is specifically required in ensheathing glia to regulate head bending and peristalsis. shopper mutants show elevated sulfite levels affecting the glutamate homeostasis which then act on neuronal network function. Interestingly, human patients lacking the Shopper homolog SUOX develop neurological symptoms, including seizures. Given an enhanced expression of SUOX by oligodendrocytes, our findings might indicate that in both invertebrates and vertebrates more than one glial cell type may be involved in modulating neuronal activity.
One of the processes that may play a key role in plant species coexistence and ecosystem functioning is plant–soil feedback, the effect of plants on associated soil communities and the resulting feedback on plant performance. Plant–soil feedback at the interspecific level (comparing growth on own soil with growth on soil from different species) has been studied extensively, while plant–soil feedback at the intraspecific level (comparing growth on own soil with growth on soil from different accessions within a species) has only recently gained attention. Very few studies have investigated the direction and strength of feedback among different taxonomic levels, and initial results have been inconclusive, discussing phylogeny, and morphology as possible determinants. To test our hypotheses that the strength of negative feedback on plant performance increases with increasing taxonomic level and that this relationship is explained by morphological similarities, we conducted a greenhouse experiment using species assigned to three taxonomic levels (intraspecific, interspecific, and functional group level). We measured certain fitness‐related aboveground traits and used them along literature‐derived traits to determine the influence of morphological similarities on the strength and direction of the feedback. We found that the average strength of negative feedback increased from the intraspecific over the interspecific to the functional group level. However, individual accessions and species differed in the direction and strength of the feedback. None of our results could be explained by morphological dissimilarities or individual traits. Synthesis. Our results indicate that negative plant–soil feedback is stronger if the involved plants belong to more distantly related species. We conclude that the taxonomic level is an important factor in the maintenance of plant coexistence with plant–soil feedback as a potential stabilizing mechanism and should be addressed explicitly in coexistence research, while the traits considered here seem to play a minor role.
This study adopts a cognitive approach to the analysis of the use of the Spanish imperfecto as a construal form for the conceptualization of state of affairs in certain journalistic texts. In doing so, the main focus of the study is to investigate cognitive processes like modalization and subjectivization, which are related to the speaker’s standpoint and to his subjective, not grammatically motivated, decision to use the imperfective instead of the perfective form. By the help of the corpus programmes GlossaNet and CREA (corpus of the Real Academia Española) we analyze the imperfective use of some Spanish verbs, which are semantically perfective in nature so that the normative use would require a perfective form. In other words, we investigate how the speaker/journalist construes a reality or situation to be expressed by means of the imperfecto and show that this use of the imperfect is typical for journalistic discourse.
In the here presented work we discuss a series of results that are all in one way or another connected to the phenomenon of trapping in black hole spacetimes.
First we present a comprehensive review of the Kerr-Newman-Taub-NUT-de-Sitter family of black hole spacetimes and their most important properties. From there we go into a detailed analysis of the bahaviour of null geodesics in the exterior region of a sub-extremal Kerr spacetime. We show that most well known fundamental properties of null geodesics can be represented in one plot. In particular, one can see immediately that the ergoregion and trapping are separated in phase space.
We then consider the sets of future/past trapped null geodesics in the exterior region of a sub-extremal Kerr-Newman-Taub-NUT spacetime. We show that from the point of view of any timelike observer outside of such a black hole, trapping can be understood as two smooth sets of spacelike directions on the celestial sphere of the observer. Therefore the topological structure of the trapped set on the celestial sphere of any observer is identical to that in Schwarzschild.
We discuss how this is relevant to the black hole stability problem.
In a further development of these observations we introduce the notion of what it means for the shadow of two observers to be degenerate. We show that, away from the axis of symmetry, no continuous degeneration exists between the shadows of observers at any point in the exterior region of any Kerr-Newman black hole spacetime of unit mass. Therefore, except possibly for discrete changes, an observer can, by measuring the black holes shadow, determine the angular momentum and the charge of the black hole under observation, as well as the observer's radial position and angle of elevation above the equatorial plane. Furthermore, his/her relative velocity compared to a standard observer can also be measured. On the other hand, the black hole shadow does not allow for a full parameter resolution in the case of a Kerr-Newman-Taub-NUT black hole, as a continuous degeneration relating specific angular momentum, electric charge, NUT charge and elevation angle exists in this case.
We then use the celestial sphere to show that trapping is a generic feature of any black hole spacetime.
In the last chapter we then prove a generalization of the mode stability result of Whiting (1989) for the Teukolsky equation for the case of real frequencies. The main result of the last chapter states that a separated solution of the Teukolsky equation governing massless test fields on the Kerr spacetime, which is purely outgoing at infinity, and purely ingoing at the horizon, must vanish. This has the consequence, that for real frequencies, there are linearly independent fundamental solutions of the radial Teukolsky equation which are purely ingoing at the horizon, and purely outgoing at infinity, respectively. This fact yields a representation formula for solutions of the inhomogenous Teukolsky equation, and was recently used by Shlapentokh-Rothman (2015) for the scalar wave equation.
The newly collected “Potsdam Grievance Statistics File” (PGSF) holds data on the number and topics of grievances (“Eingaben”) that were addressed to local authorities of the German Democratic Republic (GDR) in the years 1970 to 1989. The PGSF allows quantitative analyses on topics such as participation, quality of life, and value change in the German Democratic Republic. This paper introduces the concepts of the data set and discusses the validity of its contents.
This paper assesses, both quantitatively and qualitatively, the work of the Peace and Security Council (PSC) of the African Union (AU) with respect to peace support operations. It seeks to know whether the establishment of the PSC in 2002 is leading or has led to a rise or a decline of collective security in Africa. It is demonstrated that in regard to its relative legal and institutional robustness, the PSC can be perceived as a rise of collective security compared with its predecessor, the Central Organ of the Organisation of African Unity (OAU). However, it stagnates in terms of quantity and quality of actions on the ground. The main problem lies in the lack of sufficient operational autonomy from member states and international partners, such as the United Nations. Therefore, the PSC’s contribution to the maintenance of peace and security, and so the rise of the international rule of law in Africa is limited. The continent is still a war-torn region, affected by political crises and the expansion of terrorism in many countries. To solve this problem, AU member states should strengthen the PSC’s capacity, starting with the quick operationalisation of the African Standby Force. The implementation of the 2016 decision on alternative sources of financing AU’s institutions and activities is also a priority. In this regard, the political will of African states that may show that they want to take their organisation more seriously is required. This can further the AU self-reliance policy in collective security though the promotion of African solutions to African problems, and reduce the burden of the United Nations and other non-African actors’ interventions in the continent.
Serious knee pain and related disability have an annual prevalence of approximately 25% on those over the age of 55 years. As curative treatments for the common knee problems are not available to date, knee pathologies typically progress and often lead to osteoarthritis (OA). While the roles that the meniscus plays in knee biomechanics are well characterized, biological mechanisms underlying meniscus pathophysiology and roles in knee pain and OA progression are not fully clear. Experimental treatments for knee disorders that are successful in animal models often produce unsatisfactory results in humans due to species differences or the inability to fully replicate disease progression in experimental animals. The use of animals with spontaneous knee pathologies, such as dogs, can significantly help addressing this issue. As microscopic and macroscopic anatomy of the canine and human menisci are similar, spontaneous meniscal pathologies in canine patients are thought to be highly relevant for translational medicine. However, it is not clear whether the biomolecular mechanisms of pain, degradation of extracellular matrix, and inflammatory responses are species dependent. The aims of this review are (1) to provide an overview of the anatomy, physiology, and pathology of the human and canine meniscus, (2) to compare the known signaling pathways involved in spontaneous meniscus pathology between both species, and (3) to assess the relevance of dogs with spontaneous meniscal pathology as a translational model. Understanding these mechanisms in human and canine meniscus can help to advance diagnostic and therapeutic strategies for painful knee disorders and improve clinical decision making.
Leaf senescence is an essential physiological process in plants that supports the recycling of nitrogen and other nutrients to support the growth of developing organs, including young leaves, seeds, and fruits. Thus, the regulation of senescence is crucial for evolutionary success in wild populations and for increasing yield in crops. Here, we describe the influence of a NAC transcription factor, SlNAP2 (Solanum lycopersicum NAC-like, activated by Apetala3/Pistillata), that controls both leaf senescence and fruit yield in tomato (S. lycopersicum). SlNAP2 expression increases during age-dependent and dark-induced leaf senescence. We demonstrate that SlNAP2 activates SlSAG113 (S. lycopersicum SENESCENCE-ASSOCIATED GENE113), a homolog of Arabidopsis (Arabidopsis thaliana) SAG113, chlorophyll degradation genes such as SlSGR1 (S. lycopersicum senescence-inducible chloroplast stay-green protein 1) and SlPAO (S. lycopersicum pheide a oxygenase), and other downstream targets by directly binding to their promoters, thereby promoting leaf senescence. Furthermore, SlNAP2 directly controls the expression of genes important for abscisic acid (ABA) biosynthesis, S. lycopersicum 9-cis-epoxycarotenoid dioxygenase 1 (SlNCED1); transport, S. lycopersicum ABC transporter G family member 40 (SlABCG40); and degradation, S. lycopersicum ABA 8'-hydroxylase (SlCYP707A2), indicating that SlNAP2 has a complex role in establishing ABA homeostasis during leaf senescence. Inhibiting SlNAP2 expression in transgenic tomato plants impedes leaf senescence but enhances fruit yield and sugar content likely due to prolonged leaf photosynthesis in aging tomato plants. Our data indicate that SlNAP2 has a central role in controlling leaf senescence and fruit yield in tomato.
While the role of and consequences of being a bystander to face-to-face bullying has received some attention in the literature, to date, little is known about the effects of being a bystander to cyberbullying. It is also unknown how empathy might impact the negative consequences associated with being a bystander of cyberbullying. The present study focused on examining the longitudinal association between bystander of cyberbullying depression, and anxiety, and the moderating role of empathy in the relationship between bystander of cyberbullying and subsequent depression and anxiety. There were 1,090 adolescents (M-age = 12.19; 50% female) from the United States included at Time 1, and they completed questionnaires on empathy, cyberbullying roles (bystander, perpetrator, victim), depression, and anxiety. One year later, at Time 2, 1,067 adolescents (M-age = 13.76; 51% female) completed questionnaires on depression and anxiety. Results revealed a positive association between bystander of cyberbullying and depression and anxiety. Further, empathy moderated the positive relationship between bystander of cyberbullying and depression, but not for anxiety. Implications for intervention and prevention programs are discussed.
Experimental studies on polysemy have come to contradictory conclusions on whether words with multiple senses are stored as separate or shared mental representations. The present study examined the semantic relatedness and semantic similarity of literal and non-literal (metonymic and metaphorical) senses of three word classes: nouns, verbs, and adjectives. Two methods were used: a psycholinguistic experiment and a distributional analysis of corpus data. In the experiment, participants were presented with 6-12 short phrases containing a polysemous word in literal, metonymic, or metaphorical senses and were asked to classify them so that phrases with the same perceived sense were grouped together. To investigate the impact of professional background on their decisions, participants were controlled for linguistic vs. non-linguistic education. For nouns and verbs, all participants preferred to group together phrases with literal and metonymic senses, but not any other pairs of senses. For adjectives, two pairs of senses were often grouped together: literal with metonymic, and metonymic with metaphorical. Participants with a linguistic background were more accurate than participants with non-linguistic backgrounds, although both groups shared principal patterns of sense classification. For the distributional analysis of corpus data, we used a semantic vector approach to quantify the similarity of phrases with literal, metonymic, and metaphorical senses in the corpora. We found that phrases with literal and metonymic senses had the highest degree of similarity for the three word classes, and that metonymic and metaphorical senses of adjectives had the highest degree of similarity among all word classes. These findings are in line with the experimental results. Overall, the results suggest that the mental representation of a polysemous word depends on its word class. In nouns and verbs, literal and metonymic senses are stored together, while metaphorical senses are stored separately; in adjectives, metonymic senses significantly overlap with both literal and metaphorical senses.
The Making of Tupaia’s Map
(2018)
Tupaia’s Map is one of the most famous and enigmatic artefacts to emerge from the early encounters between Europeans and Pacific Islanders. It was drawn by Tupaia, an arioi priest, chiefly advisor and master navigator from Ra‘iātea in the Leeward Society Islands in collaboration with various members of the crew of James Cook’s Endeavour, in two distinct moments of mapmaking and three draft stages between August 1769 and February 1770. To this day, the identity of many islands on the chart, and the logic of their arrangement have posed a riddle to researchers. Drawing in part on archival material hitherto overlooked, in this long essay we propose a new understanding of the chart’s cartographic logic, offer a detailed reconstruction of its genesis, and thus for the first time present a comprehensive reading of Tupaia’s Map. The chart not only underscores the extent and mastery of Polynesian navigation, it is also a remarkable feat of translation between two very different wayfinding systems and their respective representational models.
Background
Due to inconclusive evidence on the effects of foot orthoses treatment on lower limb kinematics and kinetics in children, studies are needed that particularly evaluate the long-term use of foot orthoses on lower limb alignment during walking. Thus, the main objective of this study was to evaluate the effects of long-term treatment with arch support foot orthoses versus a sham condition on lower extremity kinematics and kinetics during walking in children with flexible flat feet.
Methods
Thirty boys aged 8–12 years with flexible flat feet participated in this study. While the experimental group (n = 15) used medial arch support foot orthoses during everyday activities over a period of four months, the control group (n = 15) received flat 2-mm-thick insoles (i.e., sham condition) for the same time period. Before and after the intervention period, walking kinematics and ground reaction forces were collected.
Results
Significant group by time interactions were observed during walking at preferred gait speed for maximum ankle eversion, maximum ankle internal rotation angle, minimum knee abduction angle, maximum knee abduction angle, maximum knee external rotation angle, maximum knee internal rotation angle, maximum hip extension angle, and maximum hip external rotation angle in favor of the foot orthoses group. In addition, statistically significant group by time interactions were detected for maximum posterior, and vertical ground reaction forces in favor of the foot orthoses group.
Conclusions
The long-term use of arch support foot orthoses proved to be feasible and effective in boys with flexible flat feet to improve lower limb alignment during walking.
The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol
(2018)
Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.
Abstract
Background
The unisexual Amazon molly (Poecilia formosa) originated from a hybridization between two sexual species, the sailfin molly (Poecilia latipinna) and the Atlantic molly (Poecilia mexicana). The Amazon molly reproduces clonally via sperm-dependent parthenogenesis (gynogenesis), in which the sperm of closely related species triggers embryogenesis of the apomictic oocytes, but typically does not contribute genetic material to the next generation. We compare for the first time the gonadal transcriptome of the Amazon molly to those of both ancestral species, P. mexicana and P. latipinna.
Results
We sequenced the gonadal transcriptomes of the P. formosa and its parental species P. mexicana and P. latipinna using Illumina RNA-sequencing techniques (paired-end, 100 bp). De novo assembly of about 50 million raw read pairs for each species was performed using Trinity, yielding 106,922 transcripts for P. formosa, 115,175 for P. latipinna, and 133,025 for P. mexicana after eliminating contaminations. On the basis of sequence similarity comparisons to other teleost species and the UniProt databases, functional annotation, and differential expression analysis, we demonstrate the similarity of the transcriptomes among the three species. More than 40% of the transcripts for each species were functionally annotated and about 70% were assigned to orthologous genes of a closely related species. Differential expression analysis between the sexual and unisexual species uncovered 2035 up-regulated and 564 down-regulated genes in P. formosa. This was exemplary validated for six genes by qRT-PCR.
Conclusions
We identified more than 130 genes related to meiosis and reproduction within the apomictically reproducing P. formosa. Overall expression of these genes seems to be down-regulated in the P. formosa transcriptome compared to both ancestral species (i.e., 106 genes down-regulated, 29 up-regulated). A further 35 meiosis and reproduction related genes were not found in the P. formosa transcriptome, but were only expressed in the sexual species. Our data support the hypothesis of general down-regulation of meiosis-related genes in the apomictic Amazon molly. Furthermore, the obtained dataset and identified gene catalog will serve as a resource for future research on the molecular mechanisms behind the reproductive mode of this unisexual species.
This paper illustrates the functional and conceptual variances of law in different contexts. Whereas legal actors on the international level might normatively aim for law to have a similar effect to that of domestic law, the way in which international and supranational law can fulfil these potential functions is different. Accordingly, this paper argues that an awareness with regard to the particularities and challenges that the potential functions of law encounter in the international and supranational context is needed. Moreover, it suggests an analytical lens to conceptually frame and locate current developments, offering a broader perspective on, or even an element of explication for, the apparent crisis that law is currently facing on the international and supranational scale. After describing the potential functions of law on an abstract scale and grouping them into analytical categories, the paper uses these categories as a lens in order to assess in which way international law can fulfil these potential functions, where priorities regarding certain functions might differ and where some aspects of these functions are challenged when law is made and applied in the international and supranational sphere.
There are 63 known species of Thecaphora (Glomosporiaceae, Ustilaginomycotina), a third of which occur on Asteraceae. These smut fungi produce yellowish-brown to reddish-brown masses of spore balls in specific, mostly regenerative, plant organs. A species of Thecaphora was collected in the flower heads of Anthemis chia (Anthemideae, Asteraceae) on Rhodes Island, Greece, in 2015 and 2017, which represents the first smut record of a smut fungus on a host plant species in this tribe. Based on its distinctive morphology, host species and genetic divergence, this species is described as Thecaphora anthemidis sp. nov. Molecular barcodes of the ITS region are provided for this and several other species of Thecaphora. A phylogenetic and morphological comparison to closely related species showed that Th. anthemidis differed from other species of Thecaphora. Thecaphora anthemidis produced loose spore balls in the flower heads and peduncles of Anthemis chia unlike other flower-infecting species.
Combining training of muscle strength and cardiorespiratory fitness within a training cycle could increase athletic performance more than single-mode training. However, the physiological effects produced by each training modality could also interfere with each other, improving athletic performance less than single-mode training. Because anthropometric, physiological, and biomechanical differences between young and adult athletes can affect the responses to exercise training, young athletes might respond differently to concurrent training (CT) compared with adults. Thus, the aim of the present systematic review with meta-analysis was to determine the effects of concurrent strength and endurance training on selected physical fitness components and athletic performance in youth. A systematic literature search of PubMed and Web of Science identified 886 records. The studies included in the analyses examined children (girls age 6–11 years, boys age 6–13 years) or adolescents (girls age 12–18 years, boys age 14–18 years), compared CT with single-mode endurance (ET) or strength training (ST), and reported at least one strength/power—(e.g., jump height), endurance—(e.g., peak V°O2, exercise economy), or performance-related (e.g., time trial) outcome. We calculated weighted standardized mean differences (SMDs). CT compared to ET produced small effects in favor of CT on athletic performance (n = 11 studies, SMD = 0.41, p = 0.04) and trivial effects on cardiorespiratory endurance (n = 4 studies, SMD = 0.04, p = 0.86) and exercise economy (n = 5 studies, SMD = 0.16, p = 0.49) in young athletes. A sub-analysis of chronological age revealed a trend toward larger effects of CT vs. ET on athletic performance in adolescents (SMD = 0.52) compared with children (SMD = 0.17). CT compared with ST had small effects in favor of CT on muscle power (n = 4 studies, SMD = 0.23, p = 0.04). In conclusion, CT is more effective than single-mode ET or ST in improving selected measures of physical fitness and athletic performance in youth. Specifically, CT compared with ET improved athletic performance in children and particularly adolescents. Finally, CT was more effective than ST in improving muscle power in youth.
This thesis investigates the comprehension of the passive voice in three distinct populations. First, the comprehension of passives by adult German speakers was studied, followed by an examination of how German-speaking children comprehend the structure. Finally, bilingual Mandarin-English speakers were tested on their comprehension of the passive voice in English, which is their L2. An integral part of testing the comprehension in all three populations is the use of structural priming. In each of the three distinct parts of the research, structural priming was used for a specific reason. In the study involving adult German speakers, productive and receptive structural priming was directly compared. The goal was to see the effect the two priming modalities have on language comprehension. In the study on German-acquiring children, structural priming was an important tool in answering the question regarding the delayed acquisition of the passive voice. Finally, in the study on the bilingual population, cross-linguistic priming was used to investigate the importance of word order in the priming effect, since Mandarin and English have different word orders in passive voice sentences.
The complete mitochondrial genome of the common vole, Microtus arvalis (Rodentia: Arvicolinae)
(2018)
The common vole, Microtus arvalis belongs to the genus Microtus in the subfamily Arvicolinae. In this study, the complete mitochondrial genome of M. arvalis was recovered using shotgun sequencing and an iterative mapping approach using three related species. Phylogenetic analyses using the sequence of 21 arvicoline species place the common vole as a sister species to the East European vole (Microtus levis), but as opposed to previous results we find no support for the recognition of the genus Neodon within the subfamily Arvicolinae, as this is, as well as the genus Lasiopodomys, found within the Microtus genus.
Background
In health research, indicators of socioeconomic status (SES) are often used interchangeably and often lack theoretical foundation. This makes it difficult to compare results from different studies and to explore the relationship between SES and health outcomes. To aid researchers in choosing appropriate indicators of SES, this article proposes and tests a theory-based selection of SES indicators using chronic back pain as a health outcome.
Methods
Strength of relationship predictions were made using Brunner & Marmot’s model of ‘social determinants of health’. Subsequently, a longitudinal study was conducted with 66 patients receiving in-patient treatment for chronic back pain. Sociodemographic variables, four SES indicators (education, job position, income, multidimensional index) and back pain intensity and disability were obtained at baseline. Both pain dimensions were assessed again 6 months later. Using linear regression, the predictive strength of each SES indicator on pain intensity and disability was estimated and compared to the theory based prediction.
Results
Chronic back pain intensity was best predicted by the multidimensional index (beta = 0.31, p < 0.05), followed by job position (beta = 0.29, p < 0.05) and education (beta = −0.29, p < 0.05); whereas, income exerted no significant influence. Back pain disability was predicted strongest by education (beta = −0.30, p < 0.05) and job position (beta = 0.29, p < 0.05). Here, multidimensional index and income had no significant influence.
Conclusions
The choice of SES indicators influences predictive power on both back pain dimensions, suggesting SES predictors cannot be used interchangeably. Therefore, researchers should carefully consider prior to each study which SES indicator to use. The introduced framework can be valuable in supporting this decision because it allows for a stable prediction of SES indicator influence and their hierarchy on a specific health outcomes.
The social context plays a decisive role in the formation of the academic self-concept (ASC) and has been widely studied as the big-fish-little-pond-effect (BFLPE). This effect describes that comparable talented students in high-achieving school settings have a lower ASC compared to equally talented students attending low-achieving settings. Past research has focused on students' domain-specific ASC, while little is known about the relation of achievement-related classroom compositions and the various facets of ASC. Additionally, BFLPE-research has been critiqued to build its theoretical frame on social comparison theory, without providing sufficient empirical support. To address this gap, we analyzed how the single student's social, criterial, absolute, and individual ASC relate to class-level achievement of 8th graders. Applying Multilevel Structural Equation Modeling (MLSEM) we found that all facets of ASC were significantly related to average-class achievement, while student's social ASC revealed the strongest associated. The results reveal explicitly that average-class achievement is strongly related to social comparison processes.
Concrete-operational thinking depicts an important aspect of cognitive development. A promising approach in promoting these skills is the instruction of strategies. The construction of such instructional programs requires insights into the mental operations involved in problem-solving. In the present paper, we address the question to which extent variations of the effect of isolated and combined mental operations (strategies) on correct solution of concrete-operational concepts can be observed. Therefore, a cross-sectional design was applied. The use of mental operations was measured by thinking-aloud reports from 80 first- and second-graders (N = 80) while solving tasks depicting concrete-operational thinking. Concrete-operational thinking was assessed using the subscales conservation of numbers, classification and sequences of the TEKO. The verbal reports were transcribed and coded with regard to the mental operations applied per task. Data analyses focused on tasks level, resulting in the analyses of N = 240 tasks per subscale. Differences regarding the contribution of isolated and combined mental operations (strategies) to correct solution were observed. Thereby, the results indicate the necessity of selection and integration of appropriate mental operations as strategies. The results offer insights in involved mental operations while solving concrete-operational tasks and depict a contribution to the construction of instructional programs.
The regular monitoring of physical fitness and sport-specific performance is important in elite sports to increase the likelihood of success in competition. This study aimed to systematically review and to critically appraise the methodological quality, validation data, and feasibility of the sport-specific performance assessment in Olympic combat sports like amateur boxing, fencing, judo, karate, taekwondo, and wrestling. A systematic search was conducted in the electronic databases PubMed, Google-Scholar, and Science-Direct up to October 2017. Studies in combat sports were included that reported validation data (e.g., reliability, validity, sensitivity) of sport-specific tests. Overall, 39 studies were eligible for inclusion in this review. The majority of studies (74%) contained sample sizes <30 subjects. Nearly, 1/3 of the reviewed studies lacked a sufficient description (e.g., anthropometrics, age, expertise level) of the included participants. Seventy-two percent of studies did not sufficiently report inclusion/exclusion criteria of their participants. In 62% of the included studies, the description and/or inclusion of a familiarization session (s) was either incomplete or not existent. Sixty-percent of studies did not report any details about the stability of testing conditions. Approximately half of the studies examined reliability measures of the included sport-specific tests (intraclass correlation coefficient [ICC] = 0.43–1.00). Content validity was addressed in all included studies, criterion validity (only the concurrent aspect of it) in approximately half of the studies with correlation coefficients ranging from r = −0.41 to 0.90. Construct validity was reported in 31% of the included studies and predictive validity in only one. Test sensitivity was addressed in 13% of the included studies. The majority of studies (64%) ignored and/or provided incomplete information on test feasibility and methodological limitations of the sport-specific test. In 28% of the included studies, insufficient information or a complete lack of information was provided in the respective field of the test application. Several methodological gaps exist in studies that used sport-specific performance tests in Olympic combat sports. Additional research should adopt more rigorous validation procedures in the application and description of sport-specific performance tests in Olympic combat sports.
Purpose
To test whether the negative relationship between perceived stress and quality of life (Hypothesis 1) can be buffered by perceived social support in patients with dementia as well as in caregivers individually (Hypothesis 2: actor effects) and across partners (Hypothesis 3: partner effects and actor-partner effects).
Method
A total of 108 couples (N = 216 individuals) comprised of one individual with early-stage dementia and one caregiving partner were assessed at baseline and one month apart. Moderation effects were investigated by applying linear mixed models and actor-partner interdependence models.
Results
Although the stress-quality of life association was more pronounced in caregivers (beta = -.63, p<.001) compared to patients (beta= -.31, p<.001), this association was equally moderated by social support in patients (beta = .14, p<.05) and in the caregivers (beta =.13, p<.05). From one partner to his or her counterpart, the partner buffering and actor-partner-buffering effect were not present.
Conclusion
The stress-buffering effect has been replicated in individuals with dementia and caregivers but not across partners. Interventions to improve quality of life through perceived social support should not only focus on caregivers, but should incorporate both partners.
Testing the Consensus Model
(2018)
The structure and definition of professional knowledge is a continuing focus of science education research. In 2012, a pedagogical content knowledge (PCK) summit was held and it suggested a model of professional knowledge and skill including PCK, which was later often called the Consensus Model (Gess-Newsome, 2015. A model of teacher professional knowledge and skill including PCK: Results of the thinking from the PCK summit. In A. Berry, P. J. Friedrichsen, & J. Loughran (Eds.), Teaching and learning in science series. Re-examining pedagogical content knowledge in science education (1st ed., pp. 28–42). New York, NY: Routledge). The Consensus Model proposes a potential powerful framework for the relations among teachers’ different professional knowledge bases, but to date it has neither been investigated empirically nor systematically. In this study, we investigated the relationships suggested by the Consensus Model among different aspects of teachers’ knowledge and skill. A sample of 35 physics teachers and their classes participated in the investigation; both teachers and their students in these classes took paper-and-pencil tests. Furthermore, a lesson taught by each of the teachers was videotaped and analysed. The video analysis focused on the interconnectedness of the content structure of the lesson as representation of the in-class actions of the teachers. The interconnectedness is understood as a direct result of the application of professional knowledge of the teachers to their teaching. The teachers’ knowledge showed no significant influence on the interconnectedness of the lesson content structure. However, the results confirmed the influence of interconnectedness and certain aspects of professional knowledge on students’ outcomes. Therefore, interconnectedness of content structure could be verified as one indicator of teachers’ instructional quality.
High-throughput sequence data retrieved from ancient or other degraded samples has led to unprecedented insights into the evolutionary history of many species, but the analysis of such sequences also poses specific computational challenges. The most commonly used approach involves mapping sequence reads to a reference genome. However, this process becomes increasingly challenging with an elevated genetic distance between target and reference or with the presence of contaminant sequences with high sequence similarity to the target species. The evaluation and testing of mapping efficiency and stringency are thus paramount for the reliable identification and analysis of ancient sequences. In this paper, we present ‘TAPAS’, (Testing of Alignment Parameters for Ancient Samples), a computational tool that enables the systematic testing of mapping tools for ancient data by simulating sequence data reflecting the properties of an ancient dataset and performing test runs using the mapping software and parameter settings of interest. We showcase TAPAS by using it to assess and improve mapping strategy for a degraded sample from a banded linsang (Prionodon linsang), for which no closely related reference is currently available. This enables a 1.8-fold increase of the number of mapped reads without sacrificing mapping specificity. The increase of mapped reads effectively reduces the need for additional sequencing, thus making more economical use of time, resources, and sample material.
Territorial reform is the most radical and contested reorganisation of local government. A sound evaluation of the outcome of such reforms is hence an important step to ensure the legitimation of any decision on the subject. However, in our view the discourse on the subject appears to be one sided, focusing primarily on overall fiscal effects scrutinised by economists. The contribution of this paper is hence threefold: Firstly, we provide an overview off territorial reforms in Europe, with a special focus on Eastern Germany as a promising case for cross-country comparisons. Secondly, we provide an over-view of the analytical classifications of these reforms and context factors to be considered in their evaluation. And thirdly, we analyse the literature on qualitative performance effects of these reforms. The results show that territorial reforms have a significant positive impact on functional performance, while the effects on participation and integration are indeed ambivalent. In doing so, we provide substantial arguments for a broader, more inclusive discussion on the success of territorial reforms.
In this study, we analyze interactions in lake and lake catchment systems of a continuous permafrost area. We assessed colored dissolved organic matter (CDOM) absorption at 440 nm (a(440)(CDOM)) and absorption slope (S300-500) in lakes using field sampling and optical remote sensing data for an area of 350 km(2) in Central Yamal, Siberia. Applying a CDOM algorithm (ratio of green and red band reflectance) for two high spatial resolution multispectral GeoEye-1 and Worldview-2 satellite images, we were able to extrapolate the a()(CDOM) data from 18 lakes sampled in the field to 356 lakes in the study area (model R-2 = 0.79). Values of a(440)(CDOM) in 356 lakes varied from 0.48 to 8.35 m(-1) with a median of 1.43 m(-1). This a()(CDOM) dataset was used to relate lake CDOM to 17 lake and lake catchment parameters derived from optical and radar remote sensing data and from digital elevation model analysis in order to establish the parameters controlling CDOM in lakes on the Yamal Peninsula. Regression tree model and boosted regression tree analysis showed that the activity of cryogenic processes (thermocirques) in the lake shores and lake water level were the two most important controls, explaining 48.4% and 28.4% of lake CDOM, respectively (R-2 = 0.61). Activation of thermocirques led to a large input of terrestrial organic matter and sediments from catchments and thawed permafrost to lakes (n = 15, mean a(440)(CDOM) = 5.3 m(-1)). Large lakes on the floodplain with a connection to Mordy-Yakha River received more CDOM (n = 7, mean a(440)(CDOM) = 3.8 m(-1)) compared to lakes located on higher terraces.
TerraSAR-X time series fill a gap in spaceborne snowmelt monitoring of small Arctic catchments
(2018)
The timing of snowmelt is an important turning point in the seasonal cycle of small Arctic catchments. The TerraSAR-X (TSX) satellite mission is a synthetic aperture radar system (SAR) with high potential to measure the high spatiotemporal variability of snow cover extent (SCE) and fractional snow cover (FSC) on the small catchment scale. We investigate the performance of multi-polarized and multi-pass TSX X-Band SAR data in monitoring SCE and FSC in small Arctic tundra catchments of Qikiqtaruk (Herschel Island) off the Yukon Coast in the Western Canadian Arctic. We applied a threshold based segmentation on ratio images between TSX images with wet snow and a dry snow reference, and tested the performance of two different thresholds. We quantitatively compared TSX- and Landsat 8-derived SCE maps using confusion matrices and analyzed the spatiotemporal dynamics of snowmelt from 2015 to 2017 using TSX, Landsat 8 and in situ time lapse data. Our data showed that the quality of SCE maps from TSX X-Band data is strongly influenced by polarization and to a lesser degree by incidence angle. VH polarized TSX data performed best in deriving SCE when compared to Landsat 8. TSX derived SCE maps from VH polarization detected late lying snow patches that were not detected by Landsat 8. Results of a local assessment of TSX FSC against the in situ data showed that TSX FSC accurately captured the temporal dynamics of different snow melt regimes that were related to topographic characteristics of the studied catchments. Both in situ and TSX FSC showed a longer snowmelt period in a catchment with higher contributions of steep valleys and a shorter snowmelt period in a catchment with higher contributions of upland terrain. Landsat 8 had fundamental data gaps during the snowmelt period in all 3 years due to cloud cover. The results also revealed that by choosing a positive threshold of 1 dB, detection of ice layers due to diurnal temperature variations resulted in a more accurate estimation of snow cover than a negative threshold that detects wet snow alone. We find that TSX X-Band data in VH polarization performs at a comparable quality to Landsat 8 in deriving SCE maps when a positive threshold is used. We conclude that TSX data polarization can be used to accurately monitor snowmelt events at high temporal and spatial resolution, overcoming limitations of Landsat 8, which due to cloud related data gaps generally only indicated the onset and end of snowmelt.
Changes in species' distributions are classically projected based on their climate envelopes. For Siberian forests, which have a tremendous significance for vegetation-climate feedbacks, this implies future shifts of each of the forest-forming larch (Larix) species to the north-east. However, in addition to abiotic factors, reliable projections must assess the role of historical biogeography and biotic interactions. Here, we use sedimentary ancient DNA and individual-based modelling to investigate the distribution of larch species and mitochondrial haplotypes through space and time across the treeline ecotone on the southern Taymyr peninsula, which at the same time presents a boundary area of two larch species. We find spatial and temporal patterns, which suggest that forest density is the most influential driver determining the precise distribution of species and mitochondrial haplotypes. This suggests a strong influence of competition on the species' range shifts. These findings imply possible climate change outcomes that are directly opposed to projections based purely on climate envelopes. Investigations of such fine-scale processes of biodiversity change through time are possible using paleoenvironmental DNA, which is available much more readily than visible fossils and can provide information at a level of resolution that is not reached in classical palaeoecology.
Material surfaces with tailored aerophobicity are crucial for applications where gas bubble wettability has to be controlled, e.g., gas storage and transport, electrodes, bioreactors or medical devices.
Here, we present switchable underwater aerophobicity of hydrophobic polymeric substrates, which respond to heat with multilevel micro- and nanotopographical changes. The cross-linked poly[ethylene-co-(vinyl acetate)] substrates possess arrays of microcylinders with a nanorough top surface. It is hypothesized that the specific micro-/nanotopography of the surface allows trapping of a water film at the micro interspace and in this way generates the aerophobic behavior. The structured substrates were programmed to a temporarily stable, nanoscale flat substrate showing aerophilic behavior. Upon heating, the topographical changes caused a switch in contact angle from aerophilic to aerophobic for approaching air bubbles. In this way, the initial adhesion of air bubbles to the programmed flat substrate could be turned into repellence for the recovered substrate surface. The temperature at which the repellence of air bubbles starts can be adjusted from 58 ± 3 °C to 73 ± 3 °C by varying the deformation temperature applied during the temperature-memory programming procedure. The presented actively switching polymeric substrates are attractive candidates for applications, where an on-demand gas bubble repellence is advantageous.
Insight into how environmental change determines the production and distribution of cyanobacterial toxins is necessary for risk assessment. Management guidelines currently focus on hepatotoxins (microcystins). Increasing attention is given to other classes, such as neurotoxins (e.g., anatoxin-a) and cytotoxins (e.g., cylindrospermopsin) due to their potency. Most studies examine the relationship between individual toxin variants and environmental factors, such as nutrients, temperature and light. In summer 2015, we collected samples across Europe to investigate the effect of nutrient and temperature gradients on the variability of toxin production at a continental scale. Direct and indirect effects of temperature were the main drivers of the spatial distribution in the toxins produced by the cyanobacterial community, the toxin concentrations and toxin quota. Generalized linear models showed that a Toxin Diversity Index (TDI) increased with latitude, while it decreased with water stability. Increases in TDI were explained through a significant increase in toxin variants such as MC-YR, anatoxin and cylindrospermopsin, accompanied by a decreasing presence of MC-LR. While global warming continues, the direct and indirect effects of increased lake temperatures will drive changes in the distribution of cyanobacterial toxins in Europe, potentially promoting selection of a few highly toxic species or strains.
Scenarios have become a key tool for supporting sustainability research on regional and global change. In this study we evaluate four regional scenario assessments: first, to explore a number of research challenges related to sustainability science and, second, to contribute to sustainability research in the specific case studies. The four case studies used commonly applied scenario approaches that are (i) a story and simulation approach with stakeholder participation in the Oum Zessar watershed, Tunisia, (ii) a participatory scenario exploration in the Rwenzori region, Uganda, (iii) a model-based prepolicy study in the Inner Niger Delta, Mali, and (iv) a model coupling-based scenario analysis in upper Thukela basin, South Africa. The scenario assessments are evaluated against a set of known challenges in sustainability science, with each challenge represented by two indicators, complemented by a survey carried out on the perception of the scenario assessments within the case study regions. The results show that all types of scenario assessments address many sustainability challenges, but that the more complex ones based on story and simulation and model coupling are the most comprehensive. The study highlights the need to investigate abrupt system changes as well as governmental and political factors as important sources of uncertainty. For an in-depth analysis of these issues, the use of qualitative approaches and an active engagement of local stakeholders are suggested. Studying ecological thresholds for the regional scale is recommended to support research on regional sustainability. The evaluation of the scenario processes and outcomes by local researchers indicates the most transparent scenario assessments as the most useful. Focused, straightforward, yet iterative scenario assessments can be very relevant by contributing information to selected sustainability problems.
Synthesis, assembly and thermo-responsivity of polymer-functionalized magnetic cobalt nanoparticles
(2018)
This thesis mainly covers the synthesis, surface modification, magnetic-field-induced assembly and thermo-responsive functionalization of superparamagnetic Co NPs initially stabilized by hydrophobic small molecules oleic acid (OA) and trioctylphosphine oxide (TOPO), as well as the synthesis of both superparamagnetic and ferromagnetic Co NPs by using end-functionalized-polystyrene as stabilizer.
Co NPs, due to their excellent magnetic and catalytic properties, have great potential application in various fields, such as ferrofluids, catalysis, and magnetic resonance imaging (MRI). Superparamagnetic Co NPs are especially interesting, since they exhibit zero coercivity. They get magnetized in an external magnetic field and reach their saturation magnetization rapidly, but no magnetic moment remains after removal of the applied magnetic field. Therefore, they do not agglomerate in the body when they are used in biomedical applications. Normally, decomposition of metallic precursors at high temperature is one of the most important methods in preparation of monodisperse magnetic NPs, providing tunability in size and shape. Hydrophobic ligands like OA, TOPO and oleylamine are often used to both control the growth of NPs and protect them from agglomeration. The as-prepared magnetic NPs can be used in biological applications as long as they are transferred into water. Moreover, their supercrystal assemblies have the potential for high density data storage and electronic devices. In addition to small molecules, polymers can also be used as surfactants for the synthesis of ferromagnetic and superparamagnetic NPs by changing the reaction conditions. Therefore, chapter 2 gives an overview on the basic concept of synthesis, surface modification and self-assembly of magnetic nanoparticles. Various examples were used to illustrate the recent work.
The hydrophobic Co NPs synthesized with small molecules as surfactants limit their biological applications, which require a hydrophilic or aqueous environment. Surface modification (e.g., ligand exchange) is a general idea for either phase transition or surface-functionalization. Therefore, in chapter 3, a ligand exchange process was conducted to functionalize the surface of Co NPs. PNIPAM is one of the most popular smart polymers and its lower critical solution temperature (LCST) is around 32 °C, with a reversible change in the conformation structure between hydrophobic and hydrophilic. The novel nanocomposites of superparamagnetic Co NPs and thermo-responsive PNIPAM are of great interest. Thus, well-defined superparamagnetic Co NPs were firstly synthesized through the thermolysis of cobalt carbonyl by using OA and TOPO as surfactants. A functional ATRP initiator, containing an amine (as anchoring group) and a 2-bromopropionate group (SI-ATRP initiator), was used to replace the original ligands. This process is rapid and facial for efficient surface functionalization and afterwards the Co NPs can be dispersed into polar solvent DMF without aggregation. FT-IR spectroscopy showed that the TOPO was completely replaced, but a small amount of OA remained on the surface. A TGA measurement allowed the calculation of the grafting density of the initiator as around 3.2 initiator/nm2. Then, the surface-initiated ATRP was conducted for the polymerization of NIPAM on the surface of Co NPs and rendered the nanocomposites water-dispersible. A temperature-dependent dynamic light scattering study showed the aggregation behavior of PNIPAM-coated Co NPs upon heating and this process was proven to be reversible. The combination of superparamagnetic and thermo-responsive properties in these hybrid nanoparticles is promising for future applications e.g. in biomedicine.
In chapter 4, the magnetic-field-induced assembly of superparamagnetic cobalt nanoparticles both on solid substrates and at liquid-air interface was investigated. OA- and TOPO-coated Co NPs were synthesized via the thermolysis of cobalt carbonyl and dispersed into either hexane or toluene. The Co NP dispersion was dropped onto substrates (e.g., TEM grid, silicon wafer) and at liquid-air (water-air or ethylene glycol-air) interface. Due to the attractive dipolar interaction, 1-D chains formed in the presence of an external magnetic field. It is known that the concentration and the strength of the magnetic field can affect the assembly behavior of superparamagnetic Co NPs. Therefore, the influence of these two parameters on the morphology of the assemblies was studied. The formed 1-D chains were shorter and flexible at either lower concentration of the Co NP dispersion or lower strength of the external magnetic field due to thermal fluctuation. However, by increasing either the concentration of the NP dispersion or the strength of the applied magnetic field, these chains became longer, thicker and straighter. The reason could be that a high concentration led to a high fraction of short dipolar chains, and their interaction resulted in longer and thicker chains under applied magnetic field. On the other hand, when the magnetic field increased, the induced moments of the magnetic nanoparticles became larger, which dominated over the thermal fluctuation. Thus, the formed short chains connected to each other and grew in length. Thicker chains were also observed through chain-chain interaction. Furthermore, the induced moments of the NPs tended to direct into one direction with increased magnetic field, thus the chains were straighter. In comparison between the assembly on substrates, at water-air interface and at ethylene glycol-air interface, the assembly of Co NPs in hexane dispersion at ethylene glycol-air interface showed the most regular and homogeneous chain structures due to the better spreading of the dispersion on ethylene glycol subphase than on water subphase and substrates. The magnetic-field-induced assembly of superparamagnetic nanoparticles could provide a powerful approach for applications in data storage and electronic devices.
Chapter 5 presented the synthesis of superparamagnetic and ferromagnetic cobalt nanoparticles through a dual-stage thermolysis of cobalt carbonyl (Co2(CO)8) by using polystyrene as surfactant. The amine end-functionalized polystyrene surfactants with different molecular weight were prepared via atom transfer radical polymerization technique. The molecular weight determination of polystyrene was conducted by gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry techniques. The results showed that, when the molecular weight distribution is low (Mw/Mn < 1.2), the measurement by GPC and MALDI-ToF MS provided nearly similar results. For example, the molecular weight of 10600 Da was obtained by MALDI-ToF MS, while GPC gave 10500 g/mol (Mw/Mn = 1.17). However, if the polymer is poly distributed, MALDI-ToF MS cannot provide an accurate value. This was exemplified for a polymer with a molecular weight of 3130 Da measured by MALDI-TOF MS, while GPC showed 2300 g/mol (Mw/Mn = 1.38). The size, size distribution and magnetic properties of the hybrid particles were different by changing either the molecular weight or concentration of the polymer surfactants. The analysis from TEM characterization showed that the size of cobalt nanoparticles stabilized with polystyrene of lower molecular weight (Mn = 2300 g/mol) varied from 12–22 nm, while the size with middle (Mn = 4500 g/mol) and higher molecular weight (Mn = 10500 g/mol) of polystyrene-coated cobalt nanoparticles showed little change. Magnetic measurements exhibited that the small cobalt particles (12 nm) were superparamagnetic, while larger particles (21 nm) were ferromagnetic and assembled into 1-D chains. The grafting density calculated from thermogravimetric analysis showed that a higher grafting density of polystyrene was obtained with lower molecular weight (Mn = 2300 g/mol) than those with higher molecular weight (Mn = 10500 g/mol). Due to the larger steric hindrance, polystyrene with higher molecular weight cannot form a dense shell on the surface of the nanoparticles, which resulted in a lower grafting density. Wide angle X-ray scattering measurements revealed the epsilon cobalt crystalline phases of both superparamagnetic Co NPs coated with polystyrene (Mn = 2300 g/mol) and ferromagnetic Co NPs coated with polystyrene (Mn = 10500 g/mol). Furthermore, a stability study showed that PS-Co NPs prepared with higher polymer concentration and polymer molecular weight exhibited a better stability.
Various ways of preparing enantiomerically pure 2-amino[6]helicene derivatives were explored. Ni(0) mediated cyclotrimerization of enantiopure triynes provided (M)- and (P)-7,8-bis(p-tolyl)hexahelicene-2-amine in >99% ee as well as its benzoderivative in >99% ee. The stereocontrol was found to be inefficient for a 2- aminobenzo[6]helicene congener with an embedded five-membered ring. Helically chiral imidazolium salts bearing one or two helicene moieties have been synthesized and applied in enantioselective [2+2+2] cyclotrimerization catalyzed by an in situ formed Ni(0)-NHC complex. The synthesis of the first helically chiral Pd- and Ru-NHC complexes and their application in enantioselective catalysis was demonstrated. The latter shows promising results in enantioselective olefin metathesis reactions. A mechanistic proposal for asymmetric ring closing metathesis is provided.
Synthesis of artificial building blocks for sortase-mediated ligation and their enzymatic linkage
(2018)
The enzyme Sortase A catalyzes the formation of a peptide bond between the recognition sequence LPXTG and an oligoglycine. While manifold ligations between proteins and various biomolecules, proteins and small synthetic molecules as well as proteins and surfaces have been reported, the aim of this thesis was to investigate the sortase-catalyzed linkage between artificial building blocks. Hence, this could pave the way for the use of sortase A for tasks from a chemical point of view and maybe even materials science.
For the proof of concept, the studied systems were kept as simple as possible at first by choosing easily accessible silica NPs and commercially available polymers. These building blocks were functionalized with peptide motifs for sortase-mediated ligation. Silica nanoparticles were synthesized with diameters of 60 and 200 nm and surface modified with C=C functionalities. Then, peptides bearing a terminal cysteine were covalently linked by means of a thiol-ene reaction. 60 nm SiO2 NPs were functionalized with pentaglycines, while peptides with LPETG motif were linked to 200 nm silica particles. Polyethyleneglycol (PEG) and poly(N isopropylacrylamide) (PNIPAM) were likewise functionalized with peptides by thiol-ene reaction between cysteine residues and C=C units in the polymer end groups. Hence, G5-PEG and PNIPAM-LPETG conjugates were obtained. With this set of building blocks, NP–polymer hybrids, NP–NP, and polymer–polymer structures were generated by sortase-mediated ligation and the product formation shown by transmission electron microscopy, MALDI-ToF mass spectrometry and dynamic light scatting, among others. Thus, the linkage of these artificial building blocks by the enzyme sortase A could be demonstrated.
However, when using commercially available polymers, the purification of the polymer–peptide conjugates was impossible and resulted in a mixture containing unmodified polymer. Therefore, strategies were developed for the own synthesis of pure peptide-polymer and polymer-peptide conjugates as building blocks for sortase-mediated ligation. The designed routes are based on preparing polymer blocks via RAFT polymerization from CTAs that are attached to N- or C-terminus, respectively, of a peptide. GG-PNIPAM was synthesized through attachment of a suitable RAFT CTA to Fmoc-GG in an esterification reaction, followed by polymerization of NIPAM and cleavage of the Fmoc protection group. Furthermore, several peptides were synthesized by solid-phase peptide synthesis. The linkage of a RAFT CTA (or
polymerization initiator) to the N-terminus of a peptide can be conducted in an automated fashion as last step in a peptide synthesizer. The synthesis of such a conjugate couldn’t be realized in the time frame of this thesis, but many promising strategies exist to continue this strategy using different coupling reagents. Such polymer building blocks can be used to synthesize protein-polymer conjugates catalyzed by sortase A and the approach can be carried on to the synthesis of block copolymers by using polymer blocks with peptide motifs on both ends.
Although the proof of concept demonstrated in this thesis only shows examples that can be also synthesized by exclusively chemical techniques, a toolbox of such building blocks will enable the future formation of new materials and pave the way for the application of enzymes in materials science. In addition to nanoparticle systems and block copolymers, this also includes combination with protein-based building blocks to form hybrid materials. Hence, sortase could become an enzymatic tool that complements established chemical linking technologies and provides specific peptide motifs that are orthogonal to all existing chemical functional groups.
Symptoms of anxiety and depression in young athletes using the Hospital Anxiety and Depression Scale
(2018)
Elite young athletes have to cope with multiple psychological demands such as training volume, mental and physical fatigue, spatial separation of family and friends or time management problems may lead to reduced mental and physical recovery. While normative data regarding symptoms of anxiety and depression for the general population is available (Hinz and Brahler, 2011), hardly any information exists for adolescents in general and young athletes in particular. Therefore, the aim of this study was to assess overall symptoms of anxiety and depression in young athletes as well as possible sex differences. The survey was carried out within the scope of the study "Resistance Training in Young Athletes" (KINGS-Study). Between August 2015 and September 2016, 326 young athletes aged (mean +/- SD) 14.3 +/- 1.6 years completed the Hospital Anxiety and Depression Scale (HAD Scale). Regarding the analysis of age on the anxiety and depression subscales, age groups were classified as follows: late childhood (12-14 years) and late adolescence (15-18 years). The participating young athletes were recruited from Olympic weight lifting, handball, judo, track and field athletics, boxing, soccer, gymnastics, ice speed skating, volleyball, and rowing. Anxiety and depression scores were (mean +/- SD) 4.3 +/- 3.0 and 2.8 +/- 2.9, respectively. In the subscale anxiety, 22 cases (6.7%) showed subclinical scores and 11 cases (3.4%) showed clinical relevant score values. When analyzing the depression subscale, 31 cases (9.5%) showed subclinical score values and 12 cases (3.7%) showed clinically important values. No significant differences were found between male and female athletes (p >= 0.05). No statistically significant differences in the HADS scores were found between male athletes of late childhood and late adolescents (p >= 0.05). To the best of our knowledge, this is the first report describing questionnaire based indicators of symptoms of anxiety and depression in young athletes. Our data implies the need for sports medical as well as sports psychiatric support for young athletes. In addition, our results demonstrated that the chronological classification concerning age did not influence HAD Scale outcomes. Future research should focus on sports medical and sports psychiatric interventional approaches with the goal to prevent anxiety and depression as well as teaching coping strategies to young athletes.
In the present work, we use symbolic regression for automated modeling of dynamical systems. Symbolic regression is a powerful and general method suitable for data-driven identification of mathematical expressions. In particular, the structure and parameters of those expressions are identified simultaneously.
We consider two main variants of symbolic regression: sparse regression-based and genetic programming-based symbolic regression. Both are applied to identification, prediction and control of dynamical systems.
We introduce a new methodology for the data-driven identification of nonlinear dynamics for systems undergoing abrupt changes. Building on a sparse regression algorithm derived earlier, the model after the change is defined as a minimum update with respect to a reference model of the system identified prior to the change. The technique is successfully exemplified on the chaotic Lorenz system and the van der Pol oscillator. Issues such as computational complexity, robustness against noise and requirements with respect to data volume are investigated.
We show how symbolic regression can be used for time series prediction. Again, issues such as robustness against noise and convergence rate are investigated us- ing the harmonic oscillator as a toy problem. In combination with embedding, we demonstrate the prediction of a propagating front in coupled FitzHugh-Nagumo oscillators. Additionally, we show how we can enhance numerical weather predictions to commercially forecast power production of green energy power plants.
We employ symbolic regression for synchronization control in coupled van der Pol oscillators. Different coupling topologies are investigated. We address issues such as plausibility and stability of the control laws found. The toolkit has been made open source and is used in turbulence control applications.
Genetic programming based symbolic regression is very versatile and can be adapted to many optimization problems. The heuristic-based algorithm allows for cost efficient optimization of complex tasks.
We emphasize the ability of symbolic regression to yield white-box models. In contrast to black-box models, such models are accessible and interpretable which allows the usage of established tool chains.
The utilization of lignin as renewable electrode material for electrochemical energy storage is a sustainable approach for future batteries and supercapacitors. The composite electrode was fabricated from Kraft lignin and conductive carbon and the charge storage contribution was determined in terms of electrical double layer (EDL) and redox reactions. The important factors at play for achieving high faradaic charge storage capacity contribute to high surface area, accessibility of redox sites in lignin and their interaction with conductive additives. A thinner layer of lignin covering the high surface area of carbon facilitates the electron transfer process with a shorter pathway from the active sites of nonconductive lignin to the current collector leading to the improvement of faradaic charge storage capacity.
Composite electrodes from lignin and carbon would be even more sustainable if the fluorinated binder can be omitted. A new route to fabricate a binder-free composite electrode from Kraft lignin and high surface area carbon has been proposed by crosslinking lignin with glyoxal. A high molecular weight of lignin is obtained to enhance both electroactivity and binder capability in composite electrodes. The order of the processing step of crosslinking lignin on the composite electrode plays a crucial role in achieving a stable electrode and high charge storage capacity. The crosslinked lignin based electrodes are promising since they allow for more stable, sustainable, halogen-free and environmentally benign devices for energy storage applications. Furthermore, improvement of the amount of redox active groups (quinone groups) in lignin is useful to enhance the capacity in lithium battery applications. Direct oxidative demethylation by cerium ammonium nitrate has been carried out under mild conditions. This proves that an increase of quinone groups is able to enhance the performance of lithium battery. Thus, lignin is a promising material and could be a good candidate for application in sustainable energy storage devices.
Recent advances in single particle tracking and supercomputing techniques demonstrate the emergence of normal or anomalous, viscoelastic diffusion in conjunction with non-Gaussian distributions in soft, biological, and active matter systems. We here formulate a stochastic model based on a generalised Langevin equation in which non-Gaussian shapes of the probability density function and normal or anomalous diffusion have a common origin, namely a random parametrisation of the stochastic force. We perform a detailed analysis demonstrating how various types of parameter distributions for the memory kernel result in exponential, power law, or power-log law tails of the memory functions. The studied system is also shown to exhibit a further unusual property: the velocity has a Gaussian one point probability density but non-Gaussian joint distributions. This behaviour is reflected in the relaxation from a Gaussian to a non-Gaussian distribution observed for the position variable. We show that our theoretical results are in excellent agreement with stochastic simulations.
Numbers are omnipresent in daily life. They vary in display format and in their meaning so that it does not seem self-evident that our brains process them more or less easily and flexibly. The present thesis addresses mental number representations in general, and specifically the impact of finger counting on mental number representations. Finger postures that result from finger counting experience are one of many ways to convey numerical information. They are, however, probably the one where the numerical content becomes most tangible. By investigating the role of fingers in adults’ mental number representations the four presented studies also tested the Embodied Cognition hypothesis which predicts that bodily experience (e.g., finger counting) during concept acquisition (e.g., number concepts) stays an immanent part of these concepts. The studies focussed on different aspects of finger counting experience. First, consistency and further details of spontaneously used finger configurations were investigated when participants repeatedly produced finger postures according to specific numbers (Study 1). Furthermore, finger counting postures (Study 2), different finger configurations (Study 2 and 4), finger movements (Study 3), and tactile finger perception (Study 4) were investigated regarding their capability to affect number processing. Results indicated that active production of finger counting postures and single finger movements as well as passive perception of tactile stimulation of specific fingers co-activated associated number knowledge and facilitated responses towards corresponding magnitudes and number symbols. Overall, finger counting experience was reflected in specific effects in mental number processing of adult participants. This indicates that finger counting experience is an immanent part of mental number representations.
Findings are discussed in the light of a novel model. The MASC (Model of Analogue and Symbolic Codes) combines and extends two established models of number and magnitude processing. Especially a symbolic motor code is introduced as an essential part of the model. It comprises canonical finger postures (i.e., postures that are habitually used to represent numbers) and finger-number associations. The present findings indicate that finger counting functions both as a sensorimotor magnitude and as a symbolic representational format and that it thereby directly mediates between physical and symbolic size. The implications are relevant both for basic research regarding mental number representations and for pedagogic practices regarding the effectiveness of finger counting as a means to acquire a fundamental grasp of numbers.
Nearly 13,000 years ago, the warming trend into the Holocene was sharply interrupted by a reversal to near glacial conditions. Climatic causes and ecological consequences of the Younger Dryas (YD) have been extensively studied, however proxy archives from the Mediterranean basin capturing this period are scarce and do not provide annual resolution. Here, we report a hydroclimatic reconstruction from stable isotopes (delta O-18, delta C-13) in subfossil pines from southern France. Growing before and during the transition period into the YD (12 900-12 600 cal BP), the trees provide an annually resolved, continuous sequence of atmospheric change. Isotopic signature of tree sourcewater (delta O-18(sw)) and estimates of relative air humidity were reconstructed as a proxy for variations in air mass origin and precipitation regime. We find a distinct increase in inter-annual variability of sourcewater isotopes (delta O-18(sw)), with three major downturn phases of increasing magnitude beginning at 12 740 cal BP. The observed variation most likely results from an amplified intensity of North Atlantic (low delta O-18(sw)) versus Mediterranean (high delta O-18(sw)) precipitation. This marked pattern of climate variability is not seen in records from higher latitudes and is likely a consequence of atmospheric circulation oscillations at the margin of the southward moving polar front.
Sub-seasonal thaw slump mass wasting is not consistently energy limited at the landscape scale
(2018)
Predicting future thaw slump activity requires a sound understanding of the atmospheric drivers and geomorphic controls on mass wasting across a range of timescales. On sub-seasonal timescales, sparse measurements indicate that mass wasting at active slumps is often limited by the energy available for melting ground ice, but other factors such as rainfall or the formation of an insulating veneer may also be relevant. To study the sub-seasonal drivers, we derive topographic changes from single-pass radar interferometric data acquired by the TanDEM-X satellites. The estimated elevation changes at 12m resolution complement the commonly observed planimetric retreat rates by providing information on volume losses. Their high vertical precision (around 30 cm), frequent observations (11 days) and large coverage (5000 km(2)) allow us to track mass wasting as drivers such as the available energy change during the summer of 2015 in two study regions. We find that thaw slumps in the Tuktoyaktuk coastlands, Canada, are not energy limited in June, as they undergo limited mass wasting (height loss of around 0 cm day 1) despite the ample available energy, suggesting the widespread presence of early season insulating snow or debris veneer. Later in summer, height losses generally increase (around 3 cm day 1), but they do so in distinct ways. For many slumps, mass wasting tracks the available energy, a temporal pattern that is also observed at coastal yedoma cliffs on the Bykovsky Peninsula, Russia. However, the other two common temporal trajectories are asynchronous with the available energy, as they track strong precipitation events or show a sudden speed-up in late August respectively. The observed temporal patterns are poorly related to slump characteristics like the headwall height. The contrasting temporal behaviour of nearby thaw slumps highlights the importance of complex local and temporally varying controls on mass wasting.
Although school climate and self-efficacy have received some attention in the literature, as correlates of students’ willingness to intervene in bullying, to date, very little is known about the potential mediating role of self-efficacy in the relationship between classroom climate and students’ willingness to intervene in bullying. To this end, the present study analyzes whether the relationship between classroom cohesion (as one facet of classroom climate) and students’ willingness to intervene in bullying situations is mediated by self-efficacy in social conflicts. This study is based on a representative stratified random sample of two thousand and seventy-one students (51.3% male), between the ages of twelve and seventeen, from twenty-four schools in Germany. Results showed that between 43% and 48% of students reported that they would not intervene in bullying. A mediation test using the structural equation modeling framework revealed that classroom cohesion and self-efficacy in social conflicts were directly associated with students’ willingness to intervene in bullying situations. Furthermore, classroom cohesion was indirectly associated with higher levels of students’ willingness to intervene in bullying situations, due to self-efficacy in social conflicts. We thus conclude that: (1) It is crucial to increase students’ willingness to intervene in bullying; (2) efforts to increase students’ willingness to intervene in bullying should promote students’ confidence in dealing with social conflicts and interpersonal relationships; and (3) self-efficacy plays an important role in understanding the relationship between classroom cohesion and students’ willingness to intervene in bullying. Recommendations are provided to help increase adolescents’ willingness to intervene in bullying and for future research.
Stuck in the past?
(2018)
After the Civil War the Spanish army functioned as a guardian of domestic order, but suffered from antiquated material and little financial means. These factors have been described as fundamental reasons for the army’s low potential wartime capability. This article draws on British and German sources to demonstrate how Spanish military culture prevented an augmented effectiveness and organisational change. Claiming that the army merely lacked funding and modern equipment, falls considerably short in grasping the complexities of military effectiveness and organisational cultures, and might prove fatal for current attempts to develop foreign armed forces in conflict or post-conflict zones.
Coronary artery disease is the most common cause of death globally and is linked to a number of risk factors including serum low density lipoprotein, high density lipoprotein, triglycerides and lipoprotein(a). Recently two proteins, angiopoietin-like protein 3 and 4, have emerged from genetic studies as being factors that significantly modulate plasma triglyceride levels and coronary artery disease. The exact function and mechanism of action of both proteins remains to be elucidated, however, mutations in these proteins results in up to 34% reduction in coronary artery disease and inhibition of function results in reduced plasma triglyceride levels. Here we report the crystal structures of the fibrinogen-like domains of both proteins. These structures offer new insights into the reported loss of function mutations, the mechanisms of action of the proteins and open up the possibility for the rational design of low molecular weight inhibitors for intervention in coronary artery disease.
Active and passive source data from two seismic experiments within the interdisciplinary project TIPTEQ (from The Incoming Plate to mega Thrust EarthQuake processes) were used to image and identify the structural and petrophysical properties (such as P- and S-velocities, Poisson's ratios, pore pressure, density and amount of fluids) within the Chilean seismogenic coupling zone at 38.25°S, where in 1960 the largest earthquake ever recorded (Mw 9.5) occurred. Two S-wave velocity models calculated using traveltime and noise tomography techniques were merged with an existing velocity model to obtain a 2D S-wave velocity model, which gathered the advantages of each individual model. In a following step, P- and S-reflectivity images of the subduction zone were obtained using different pre stack and post-stack depth migration techniques. Among them, the recent prestack line-drawing depth migration scheme yielded revealing results. Next, synthetic seismograms modelled using the reflectivity method allowed, through their input 1D synthetic P- and S-velocities, to infer the composition and rocks within the subduction zone. Finally, an image of the subduction zone is given, jointly interpreting the results from this work with results from other studies. The Chilean seismogenic coupling zone at 38.25°S shows a continental crust with highly reflective horizontal, as well as (steep) dipping events. Among them, the Lanalhue Fault Zone (LFZ), which is interpreted to be east-dipping, is imaged to very shallow depths. Some steep reflectors are observed for the first time, for example one near the coast, related to high seismicity and another one near the LFZ. Steep shallow reflectivity towards the volcanic arc could be related to a steep west-dipping reflector interpreted as fluids and/or melts, migrating upwards due to material recycling in the continental mantle wedge. The high resolution of the S-velocity model in the first kilometres allowed to identify several sedimentary basins, characterized by very low P- and S-velocities, high Poisson's ratios and possible steep reflectivity. Such high Poisson's ratios are also observed within the oceanic crust, which reaches the seismogenic zone hydrated due to bending-related faulting. It is interpreted to release water until reaching the coast and under the continental mantle wedge. In terms of seismic velocities, the inferred composition and rocks in the continental crust is in agreement with field geology observations at the surface along the proflle. Furthermore, there is no requirement to call on the existence of measurable amounts of present-day fluids above the plate interface in the continental crust of the Coastal Cordillera and the Central Valley in this part of the Chilean convergent margin. A large-scale anisotropy in the continental crust and upper mantle, previously proposed from magnetotelluric studies, is proposed from seismic velocities. However, quantitative studies on this topic in the continental crust of the Chilean seismogenic zone at 38.25°S do not exist to date.
Amorphous calcium carbonate(ACC) is a wide spread biological material found in many organisms, such as sea Urchins and mollusks, where it serves as either a precursor phase for the crystalline biominerals or is stabilized and used in the amorphous state. As ACC readily crystallizes, stabilizers such as anions, cations or macromolecules are often present to avoid or delay unwanted crystallization. Furthermore, additives often control the properties of the materials to suit the specific function needed for the organism. E.g. cystoliths in leaves that scatter light to optimize energy uptake from the sun or calcite/aragonite crystals used in protective shells in mussels and gastropods. Lifetime of the amorphous phase is controlled by the kinetic stability against crystallization. This has often been linked to water which plays a role in the mobility of ions and hence the probability of forming crystalline nuclei to initiate crystallization. However, it is unclear how the water molecules are incorporated within the amorphous phase, either as liquid confined in pores, as structural water binding to the ions or as a mixture of both. It is also unclear how this is perturbed when additives are added, especially Mg2+, one the most common additives found in biogenic samples. Mg2+ are expected to have a strong influence on the water incorporated into ACC, given the high energy barrier to dehydration of magnesium ions compared to calcium ions in solution.
During the last 10-15 years, there has been a large effort to understand the local environment of the ions/molecules and how this affects the properties of the amorphous phase. But only a few aspects of the structure have so far been well-described in literature. The reason for this is partly caused by the low stability of ACC if exposed to air, where it tends to crystallize within minutes and by the limited quantities of ACC produced in traditional synthesis routes. A further obstacle has been the difficulty in modeling the local structure based on experimental data. To solve the problem of stability and sample size, a few studies have used stabilizers such as Mg2+ or OH- and severely dehydrated samples so as to stabilize the amorphous state, allowing for combined neutron and x-ray analysis to be performed. However, so far, a clear description of the local environments of water present in the structure has not been reported.
In this study we show that ACC can be synthesized without any stabilizing additives in quantities necessary for neutron measurements and that accurate models can be derived with the help of empirical-potential structural refinement. These analyses have shown that there is a wide range of local environments for all of the components in the system suggesting that the amorphous phase is highly inhomogeneous, without any phase separation between ions and water. We also showed that the water in ACC is mainly structural and that there is no confined or liquid-like water present in the system. Analysis of amorphous magnesium carbonate also showed that there is a large difference in the local structure of the two cations and that Mg2+ surprisingly interacts with significantly less water molecules then Ca2+ despite the higher dehydration energy. All in all, this shows that the role of water molecules as a structural component of ACC, with a strong binding to cat- and anions probably retard or prevents the crystallization of the amorphous phase.
The interaction between surfaces displaying end-grafted hydrophilic polymer brushes plays important roles in biology and in many wet-technological applications. The outer surfaces of Gram-negative bacteria, for example, are composed of lipopolysaccharide (LPS) molecules exposing oligo- and polysaccharides to the aqueous environment. This unique, structurally complex biological interface is of great scientific interest as it mediates the interaction of bacteria with neighboring bacteria in colonies and biofilms. The interaction between polymer-decorated surfaces is generally coupled to the distance-dependent conformation of the polymer chains. Therefore, structural insight into the interacting surfaces is a prerequisite to understand the interaction characteristics as well as the underlying physical mechanisms. This problem has been addressed by theory, but accurate experimental data on polymer conformations under confinement are rare, because obtaining perturbation-free structural insight into buried soft interfaces is inherently difficult.
In this thesis, lipid membrane surfaces decorated with hydrophilic polymers of technological and biological relevance are investigated under controlled interaction conditions, i.e., at defined surface separations. For this purpose, dedicated sample architectures and experimental tools are developed. Via ellipsometry and neutron reflectometry pressure-distance curves and distance-dependent polymer conformations in terms of brush compression and reciprocative interpenetration are determined. Additional element-specific structural insight into the end-point distribution of interacting brushes is obtained by standing-wave x-ray fluorescence (SWXF).
The methodology is first established for poly[ethylene glycol] (PEG) brushes of defined length and grafting density. For this system, neutron reflectometry revealed pronounced brush interpenetration, which is not captured in common brush theories and therefore motivates rigorous simulation-based treatments. In the second step the same approach is applied to realistic mimics of the outer surfaces of Gram-negative bacteria: monolayers of wild type LPSs extracted from E. Coli O55:B5 displaying strain-specific O-side chains. The neutron reflectometry experiments yield unprecedented structural insight into bacterial interactions, which are of great relevance for the properties of biofilms.
Understanding of wave environments is critical for the understanding of how particles are accelerated and lost in space. This study shows that in the vicinity of Europa and Ganymede, that respectively have induced and internal magnetic fields, chorus wave power is significantly increased. The observed enhancements are persistent and exceed median values of wave activity by up to 6 orders of magnitude for Ganymede. Produced waves may have a pronounced effect on the acceleration and loss of particles in the Jovian magnetosphere and other astrophysical objects. The generated waves are capable of significantly modifying the energetic particle environment, accelerating particles to very high energies, or producing depletions in phase space density. Observations of Jupiter's magnetosphere provide a unique opportunity to observe how objects with an internal magnetic field can interact with particles trapped in magnetic fields of larger scale objects.
The genesis of chronic pain is explained by a biopsychosocial model. It hypothesizes an interdependency between environmental and genetic factors provoking aberrant long-term changes in biological and psychological regulatory systems. Physiological effects of psychological and physical stressors may play a crucial role in these maladaptive processes. Specifically, long-term demands on the stress response system may moderate central pain processing and influence descending serotonergic and noradrenergic signals from the brainstem, regulating nociceptive processing at the spinal level. However, the underlying mechanisms of this pathophysiological interplay still remain unclear. This paper aims to shed light on possible pathways between physical (exercise) and psychological stress and the potential neurobiological consequences in the genesis and treatment of chronic pain, highlighting evolving concepts and promising research directions in the treatment of chronic pain. Two treatment forms (exercise and mindfulness-based stress reduction as exemplary therapies), their interaction, and the dose-response will be discussed in more detail, which might pave the way to a better understanding of alterations in the pain matrix and help to develop future prevention and therapeutic concepts
We provide a detailed stochastic description of the swimming motion of an E. coli bacterium in two dimension, where we resolve tumble events in time. For this purpose, we set up two Langevin equations for the orientation angle and speed dynamics. Calculating moments, distribution and autocorrelation functions from both Langevin equations and matching them to the same quantities determined from data recorded in experiments, we infer the swimming parameters of E. coli. They are the tumble rate lambda, the tumble time r(-1), the swimming speed v(0), the strength of speed fluctuations sigma, the relative height of speed jumps eta, the thermal value for the rotational diffusion coefficient D-0, and the enhanced rotational diffusivity during tumbling D-T. Conditioning the observables on the swimming direction relative to the gradient of a chemoattractant, we infer the chemotaxis strategies of E. coli. We confirm the classical strategy of a lower tumble rate for swimming up the gradient but also a smaller mean tumble angle (angle bias). The latter is realized by shorter tumbles as well as a slower diffusive reorientation. We also find that speed fluctuations are increased by about 30% when swimming up the gradient compared to the reversed direction.
Objectives: The use of simulated and standardized patients (SP) is widely accepted in the medical field and, from there, is beginning to disseminate into clinical psychology and psychotherapy. The purpose of this study was therefore to systematically review barriers and facilitators that should be considered in the implementation of SP interventions specific to clinical psychology and psychotherapy. Methods: Following current guidelines, a scoping review was conducted. The literature search focused on the MEDLINE,PsycINFO and Web of Science databases, including Dissertation Abstracts International. After screening for titles and abstracts,full texts were screened independently and in duplicate according to our inclusion criteria. For data extraction, a pre-defined form was piloted and used. Units of meaning with respect to barriers and facilitators were extracted and categorized inductively using content-analysis techniques. From the results, a matrix of interconnections and a network graph were compiled. Results: The 41 included publications were mainly in the fields of psychiatry and mental health nursing, as well as in training and education. The detailed category system contrasts four supercategories, i.e., which organizational and economic aspects to consider, which persons to include as eligible SPs, how to develop adequate scenarios, and how to authentically and consistently portray mental health patients.Conclusions: Publications focused especially on the interrelation between authenticity and consistency of portrayals, on how to evoke empathy in learners, and on economic and training aspects. A variety of recommendations for implementing SP programs,from planning to training, monitoring, and debriefing, is provided, for example, ethical screening of and ongoing support for SPs.
From a health and performance-related perspective, it is crucial to evaluate subjective symptoms and objective signs of acute training-induced immunological responses in young athletes. The limited number of available studies focused on immunological adaptations following aerobic training. Hardly any studies have been conducted on resistance-training induced stress responses. Therefore, the aim of this observational study was to investigate subjective symptoms and objective signs of immunological stress responses following resistance training in young athletes. Fourteen (7 females and 7 males) track and field athletes with a mean age of 16.4 years and without any symptoms of upper or lower respiratory tract infections participated in this study. Over a period of 7 days, subjective symptoms using the Acute Recovery and Stress Scale (ARSS) and objective signs of immunological responses using capillary blood markers were taken each morning and after the last training session. Differences between morning and evening sessions and associations between subjective and objective parameters were analyzed using generalized estimating equations (GEE). In post hoc analyses, daily change-scores of the ARSS dimensions were compared between participants and revealed specific changes in objective capillary blood samples. In the GEE models, recovery (ARSS) was characterized by a significant decrease while stress (ARSS) showed a significant increase between morning and evening-training sessions. A concomitant increase in white blood cell count (WBC), granulocytes (GRAN) and percentage shares of granulocytes (GRAN%) was found between morning and evening sessions. Of note, percentage shares of lymphocytes (LYM%) showed a significant decrease. Furthermore, using multivariate regression analyses, we identified that recovery was significantly associated with LYM%, while stress was significantly associated with WBC and GRAN%. Post hoc analyses revealed significantly larger increases in participants’ stress dimensions who showed increases in GRAN%. For recovery, significantly larger decreases were found in participants with decreases in LYM% during recovery. More specifically, daily change-scores of the recovery and stress dimensions of the ARSS were associated with specific changes in objective immunological markers (GRAN%, LYM%) between morning and evening-training sessions. Our results indicate that changes of subjective symptoms of recovery and stress dimensions using the ARSS were associated with specific changes in objectively measured immunological markers.
Spotlight on islands
(2018)
Groups of proximate continental islands may conceal more tangled phylogeographic patterns than oceanic archipelagos as a consequence of repeated sea level changes, which allow populations to experience gene flow during periods of low sea level stands and isolation by vicariant mechanisms during periods of high sea level stands. Here, we describe for the first time an ancient and diverging lineage of the Italian wall lizard Podarcis siculus from the western Pontine Islands. We used nuclear and mitochondrial DNA sequences of 156 individuals with the aim of unraveling their phylogenetic position, while microsatellite loci were used to test several a priori insular biogeographic models of migration with empirical data. Our results suggest that the western Pontine populations colonized the islands early during their Pliocene volcanic formation, while populations from the eastern Pontine Islands seem to have been introduced recently. The inter-island genetic makeup indicates an important role of historical migration, probably due to glacial land bridges connecting islands followed by a recent vicariant mechanism of isolation. Moreover, the most supported migration model predicted higher gene flow among islands which are geographically arranged in parallel. Considering the threatened status of small insular endemic populations, we suggest this new evolutionarily independent unit be given priority in conservation efforts.
While the impact of dietary cholesterol on the progression of atherosclerosis has probably been overestimated, increasing evidence suggests that dietary cholesterol might favor the transition from blunt steatosis to non-alcoholic steatohepatitis (NASH), especially in combination with high fat diets. It is poorly understood how cholesterol alone or in combination with other dietary lipid components contributes to the development of lipotoxicity. The current study demonstrated that liver damage caused by dietary cholesterol in mice was strongly enhanced by a high fat diet containing soybean oil-derived ω6-poly-unsaturated fatty acids (ω6-PUFA), but not by a lard-based high fat diet containing mainly saturated fatty acids. In contrast to the lard-based diet the soybean oil-based diet augmented cholesterol accumulation in hepatocytes, presumably by impairing cholesterol-eliminating pathways. The soybean oil-based diet enhanced cholesterol-induced mitochondrial damage and amplified the ensuing oxidative stress, probably by peroxidation of poly-unsaturated fatty acids. This resulted in hepatocyte death, recruitment of inflammatory cells, and fibrosis, and caused a transition from steatosis to NASH, doubling the NASH activity score. Thus, the recommendation to reduce cholesterol intake, in particular in diets rich in ω6-PUFA, although not necessary to reduce the risk of atherosclerosis, might be sensible for patients suffering from non-alcoholic fatty liver disease.