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Institute
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Many widely used observational data sets are comprised of several overlapping instrument records. While data inter-calibration techniques often yield continuous and reliable data for trend analysis, less attention is generally paid to maintaining higher-order statistics such as variance and autocorrelation. A growing body of work uses these metrics to quantify the stability or resilience of a system under study and potentially to anticipate an approaching critical transition in the system. Exploring the degree to which changes in resilience indicators such as the variance or autocorrelation can be attributed to non-stationary characteristics of the measurement process – rather than actual changes in the dynamical properties of the system – is important in this context. In this work we use both synthetic and empirical data to explore how changes in the noise structure of a data set are propagated into the commonly used resilience metrics lag-one autocorrelation and variance. We focus on examples from remotely sensed vegetation indicators such as vegetation optical depth and the normalized difference vegetation index from different satellite sources. We find that time series resulting from mixing signals from sensors with varied uncertainties and covering overlapping time spans can lead to biases in inferred resilience changes. These biases are typically more pronounced when resilience metrics are aggregated (for example, by land-cover type or region), whereas estimates for individual time series remain reliable at reasonable sensor signal-to-noise ratios. Our work provides guidelines for the treatment and aggregation of multi-instrument data in studies of critical transitions and resilience.
In this work, binding interactions between biomolecules were analyzed by a technique that is based on electrically controllable DNA nanolevers. The technique was applied to virus-receptor interactions for the first time. As receptors, primarily peptides on DNA nanostructures and antibodies were utilized. The DNA nanostructures were integrated into the measurement technique and enabled the presentation of the peptides in a controllable geometrical order. The number of peptides could be varied to be compatible to the binding sites of the viral surface proteins.
Influenza A virus served as a model system, on which the general measurability was demonstrated. Variations of the receptor peptide, the surface ligand density, the measurement temperature and the virus subtypes showed the sensitivity and applicability of the technology. Additionally, the immobilization of virus particles enabled the measurement of differences in oligovalent binding of DNA-peptide nanostructures to the viral proteins in their native environment.
When the coronavirus pandemic broke out in 2020, work on binding interactions of a peptide from the hACE2 receptor and the spike protein of the SARS-CoV-2 virus revealed that oligovalent binding can be quantified in the switchSENSE technology. It could also be shown that small changes in the amino acid sequence of the spike protein resulted in complete loss of binding. Interactions of the peptide and inactivated virus material as well as pseudo virus particles could be measured. Additionally, the switchSENSE technology was utilized to rank six antibodies for their binding affinity towards the nucleocapsid protein of SARS-CoV-2 for the development of a rapid antigen test device.
The technique was furthermore employed to show binding of a non-enveloped virus (adenovirus) and a virus-like particle (norovirus-like particle) to antibodies. Apart from binding interactions, the use of DNA origami levers with a length of around 50 nm enabled the switching of virus material. This proved that the technology is also able to size objects with a hydrodynamic diameter larger than 14 nm.
A theoretical work on diffusion and reaction-limited binding interactions revealed that the technique and the chosen parameters enable the determination of binding rate constants in the reaction-limited regime.
Overall, the applicability of the switchSENSE technique to virus-receptor binding interactions could be demonstrated on multiple examples. While there are challenges that remain, the setup enables the determination of affinities between viruses and receptors in their native environment. Especially the possibilities regarding the quantification of oligo- and multivalent binding interactions could be presented.
Selenium (Se) is an essential trace element that is ubiquitously present in the environment in small concentrations. Essential functions of Se in the human body are manifested through the wide range of proteins, containing selenocysteine as their active center. Such proteins are called selenoproteins which are found in multiple physiological processes like antioxidative defense and the regulation of thyroid hormone functions. Therefore, Se deficiency is known to cause a broad spectrum of physiological impairments, especially in endemic regions with low Se content. Nevertheless, being an essential trace element, Se could exhibit toxic effects, if its intake exceeds tolerable levels. Accordingly, this range between deficiency and overexposure represents optimal Se supply. However, this range was found to be narrower than for any other essential trace element. Together with significantly varying Se concentrations in soil and the presence of specific bioaccumulation factors, this represents a noticeable difficulty in the assessment of Se
epidemiological status. While Se is acting in the body through multiple selenoproteins, its intake occurs mainly in form of small organic or inorganic molecular mass species. Thus, Se exposure not only depends on daily intake but also on the respective chemical form, in which it is present.
The essential functions of selenium have been known for a long time and its primary forms in different food sources have been described. Nevertheless, analytical capabilities for a comprehensive investigation of Se species and their derivatives have been introduced only in the last decades. A new Se compound was identified in 2010 in the blood and tissues of bluefin tuna. It was called selenoneine (SeN) since it is an isologue of naturally occurring antioxidant ergothioneine (ET), where Se replaces sulfur. In the following years, SeN was identified in a number of edible fish species and attracted attention as a new dietary Se source and potentially strong antioxidant. Studies in populations whose diet largely relies on fish revealed that SeN
represents the main non-protein bound Se pool in their blood. First studies, conducted with enriched fish extracts, already demonstrated the high antioxidative potential of SeN and its possible function in the detoxification of methylmercury in fish. Cell culture studies demonstrated, that SeN can utilize the same transporter as ergothioneine, and SeN metabolite was found in human urine.
Until recently, studies on SeN properties were severely limited due to the lack of ways to obtain the pure compound. As a predisposition to this work was firstly a successful approach to SeN synthesis in the University of Graz, utilizing genetically modified yeasts. In the current study, by use of HepG2 liver carcinoma cells, it was demonstrated, that SeN does not cause toxic effectsup to 100 μM concentration in hepatocytes. Uptake experiments showed that SeN is not bioavailable to the used liver cells.
In the next part a blood-brain barrier (BBB) model, based on capillary endothelial cells from the porcine brain, was used to describe the possible transfer of SeN into the central nervous system (CNS). The assessment of toxicity markers in these endothelial cells and monitoring of barrier conditions during transfer experiments demonstrated the absence of toxic effects from SeN on the BBB endothelium up to 100 μM concentration. Transfer data for SeN showed slow but substantial transfer. A statistically significant increase was observed after 48 hours following SeN incubation from the blood-facing side of the barrier. However, an increase in Se content was clearly visible already after 6 hours of incubation with 1 μM of SeN. While the transfer rate of SeN after application of 0.1 μM dose was very close to that for 1 μM, incubation with 10 μM of SeN resulted in a significantly decreased transfer rate. Double-sided application of SeN caused no side-specific transfer of SeN, thus suggesting a passive diffusion mechanism of SeN across the BBB. This data is in accordance with animal studies, where ET accumulation was observed in the rat brain, even though rat BBB does not have the primary ET transporter – OCTN1. Investigation of capillary endothelial cell monolayers after incubation with SeN and reference selenium compounds showed no significant increase of intracellular selenium concentration. Speciesspecific Se measurements in medium samples from apical and basolateral compartments, as good as in cell lysates, showed no SeN metabolization. Therefore, it can be concluded that SeN may reach the brain without significant transformation.
As the third part of this work, the assessment of SeN antioxidant properties was performed in Caco-2 human colorectal adenocarcinoma cells. Previous studies demonstrated that the intestinal epithelium is able to actively transport SeN from the intestinal lumen to the blood side and accumulate SeN. Further investigation within current work showed a much higher antioxidant potential of SeN compared to ET. The radical scavenging activity after incubation with SeN was close to the one observed for selenite and selenomethionine. However, the SeN effect on the viability of intestinal cells under oxidative conditions was close to the one caused by ET. To answer the question if SeN is able to be used as a dietary Se source and induce the activity of selenoproteins, the activity of glutathione peroxidase (GPx) and the secretion of selenoprotein P (SelenoP) were measured in Caco-2 cells, additionally. As expected, reference selenium compounds selenite and selenomethionine caused efficient induction of GPx activity. In contrast to those SeN had no effect on GPx activity. To examine the possibility of SeN being embedded into the selenoproteome, SelenoP was measured in a culture medium. Even though Caco-2 cells effectively take up SeN in quantities much higher than selenite or selenomethionine, no secretion of SelenoP was observed after SeN incubation.
Summarizing, we can conclude that SeN can hardly serve as a Se source for selenoprotein synthesis. However, SeN exhibit strong antioxidative properties, which appear when sulfur in ET is exchanged by Se. Therefore, SeN is of particular interest for research not as part of Se metabolism, but important endemic dietary antioxidant.
Both horizontal-to-vertical (H/V) spectral ratios and the spatial autocorrelation method (SPAC) have proven to be valuable tools to gain insight into local site effects by ambient noise measurements. Here, the two methods are employed to assess the subsurface velocity structure at the Piano delle Concazze area on Mt Etna. Volcanic tremor records from an array of 26 broadband seismometers is processed and a strong variability of H/V ratios during periods of increased volcanic activity is found. From the spatial distribution of H/V peak frequencies, a geologic structure in the north-east of Piano delle Concazze is imaged which is interpreted as the Ellittico caldera rim. The method is extended to include both velocity data from the broadband stations and distributed acoustic sensing data from a co-located 1.5 km long fibre optic cable. High maximum amplitude values of the resulting ratios along the trajectory of the cable coincide with known faults. The outcome also indicates previously unmapped parts of a fault. The geologic interpretation is in good agreement with inversion results from magnetic survey data. Using the neighborhood algorithm, spatial autocorrelation curves obtained from the modified SPAC are inverted alone and jointly with the H/V peak frequencies for 1D shear wave velocity profiles. The obtained models are largely consistent with published models and were able to validate the results from the fibre optic cable.
In the present thesis, AC electrokinetic forces, like dielectrophoresis and AC electroosmosis, were demonstrated as a simple and fast method to functionalize the surface of nanoelectrodes with submicrometer sized biological objects. These nanoelectrodes have a cylindrical shape with a diameter of 500 nm arranged in an array of 6256 electrodes. Due to its medical relevance influenza virus as well as anti-influenza antibodies were chosen as a model organism. Common methods to bring antibodies or proteins to biosensor surfaces are complex and time-consuming. In the present work, it was demonstrated that by applying AC electric fields influenza viruses and antibodies can be immobilized onto the nanoelectrodes within seconds without any prior chemical modification of neither the surface nor the immobilized biological object. The distribution of these immobilized objects is not uniform over the entire array, it exhibits a decreasing gradient from the outer row to the inner ones. Different causes for this gradient have been discussed, such as the vortex-shaped fluid motion above the nanoelectrodes generated by, among others, electrothermal fluid flow. It was demonstrated that parts of the accumulated material are permanently immobilized to the electrodes. This is a unique characteristic of the presented system since in the literature the AC electrokinetic immobilization is almost entirely presented as a method just for temporary immobilization. The spatial distribution of the immobilized viral material or the anti-influenza antibodies at the electrodes was observed by either the combination of fluorescence microscopy and deconvolution or by super-resolution microscopy (STED). On-chip immunoassays were performed to examine the suitability of the functionalized electrodes as a potential affinity-based biosensor. Two approaches were pursued: A) the influenza virus as the bio-receptor or B) the influenza virus as the analyte. Different sources of error were eliminated by ELISA and passivation experiments. Hence, the activity of the immobilized object was inspected by incubation with the analyte. This resulted in the successful detection of anti-influenza antibodies by the immobilized viral material. On the other hand, a detection of influenza virus particles by the immobilized anti-influenza antibodies was not possible. The latter might be due to lost activity or wrong orientation of the antibodies. Thus, further examinations on the activity of by AC electric fields immobilized antibodies should follow. When combined with microfluidics and an electrical read-out system, the functionalized chips possess the potential to serve as a rapid, portable, and cost-effective point-of-care (POC) device. This device can be utilized as a basis for diverse applications in diagnosing and treating influenza, as well as various other pathogens.
The birth of the Yishuv’s national shipping company, ZIM was preceded by private enterprise; the sea had not traditionally been a focus of the Zionist movement. In the 1930s, a five-year span of private commercial shipping saw three companies in the Jewish community in Palestine – Palestine Shipping Company, Palestine Maritime Lloyd, and Atid – before shipping was cut short by the outbreak of the Second World War. Despite their brief lifespans and their negligible contribution to general shipping, these companies constituted an important milestone. Their existence helped shift the Yishuv leadership’s attitudes about shipping’s importance for the community and the need for it to be supported by national institutions.
Mothers of Seafaring
(2023)
The article aims to trace the contribution of Jewish women in the Yishuv’s maritime history. Taking the example of Henrietta Diamond, a founding member and chairperson of the Zebulun Seafaring Society, the article seeks to explore the representation and role of women in a growing Jewish maritime domain from the 1930s to the 1950s. It examines Zionist narratives on the ‘New Jew’ and the Jewish body and studies their relevance for the emerging field of maritime activities in the Yishuv. By contextualizing the work and depiction of Henrietta Diamond, the article sheds new light on the gendered notions that underlay the emergence of the Jewish maritime domain and illustrates the patterns of inclusion and exclusion in it.
Properties of Arctic aerosol in the transition between Arctic haze to summer season derived by lidar
(2023)
During the Arctic haze period, the Arctic troposphere consists of larger, yet fewer, aerosol particles than during the summer (Tunved et al., 2013; Quinn et al., 2007). Interannual variability (Graßl and Ritter, 2019; Rinke et al., 2004), as well as unknown origins (Stock et al., 2014) and properties of aerosol complicate modeling these annual aerosol cycles. This thesis investigates the modification of the microphysical properties of Arctic aerosols in the transition from Arctic haze to the summer season. Therefore, lidar measurements of Ny-Ålesund from April 2021 to the end of July 2021 are evaluated based on the aerosols’ optical properties. An overview of those properties will be provided. Furthermore, parallel radiosonde data is considered for indication of hygroscopic growth.
The annual aerosol cycle in 2021 differs from expectations based on previous studies from Tunved et al. (2013) and Quinn et al. (2007). Developments of backscatter, extinction, aerosol depolarisation, lidar ratio and color ratio show a return of the Arctic haze in May. The haze had already reduced in April, but regrew afterwards.
The average Arctic aerosol displays hygroscopic behaviour, meaning growth due to water uptake. To determine such a behaviour is generally laborious because various meteorological circumstances need to be considered. Two case studies provide further information on these possible events. In particular, a day with a rare ice cloud and with highly variable water cloud layers is observed.
The Andean Cordillera is a mountain range located at the western South American margin and is part of the Eastern- Circum-Pacific orogenic Belt. The ~7000 km long mountain range is one of the longest on Earth and hosts the second largest orogenic plateau in the world, the Altiplano-Puna plateau. The Andes are known as a non-collisional subduction-type orogen which developed as a result of the interaction between the subducted oceanic Nazca plate and the South American continental plate. The different Andean segments exhibit along-strike variations of morphotectonic provinces characterized by different elevations, volcanic activity, deformation styles, crustal thickness, shortening magnitude and oceanic plate geometry. Most of the present-day elevation can be explained by crustal shortening in the last ~50 Ma, with the shortening magnitude decreasing from ~300 km in the central (15°S-30°S) segment to less than half that in the southern part (30°S-40°S). Several factors were proposed that might control the magnitude and acceleration of shortening of the Central Andes in the last 15 Ma. One important factor is likely the slab geometry. At 27-33°S, the slab dips horizontally at ~100 km depth due to the subduction of the buoyant Juan Fernandez Ridge, forming the Pampean flat-slab. This horizontal subduction is thought to influence the thermo-mechanical state of the Sierras Pampeanas foreland, for instance, by strengthening the lithosphere and promoting the thick-skinned propagation of deformation to the east, resulting in the uplift of the Sierras Pampeanas basement blocks. The flat-slab has migrated southwards from the Altiplano latitude at ~30 Ma to its present-day position and the processes and consequences associated to its passage on the contemporaneous acceleration of the shortening rate in Central Andes remain unclear. Although the passage of the flat-slab could offer an explanation to the acceleration of the shortening, the timing does not explain the two pulses of shortening at about 15 Ma and 4 Ma that are suggested from geological observations. I hypothesize that deformation in the Central Andes is controlled by a complex interaction between the subduction dynamics of the Nazca plate and the dynamic strengthening and weakening of the South American plate due to several upper plate processes. To test this hypothesis, a detailed investigation into the role of the flat-slab, the structural inheritance of the continental plate, and the subduction dynamics in the Andes is needed. Therefore, I have built two classes of numerical thermo-mechanical models: (i) The first class of models are a series of generic E-W-oriented high-resolution 2D subduction models thatinclude flat subduction in order to investigate the role of the subduction dynamics on the temporal variability of the shortening rate in the Central Andes at Altiplano latitudes (~21°S). The shortening rate from the models was then validated with the observed tectonic shortening rate in the Central Andes. (ii) The second class of models are a series of 3D data-driven models of the present-day Pampean flat-slab configuration and the Sierras Pampeanas (26-42°S). The models aim to investigate the relative contribution of the present-day flat subduction and inherited structures in the continental lithosphere on the strain localization. Both model classes were built using the advanced finite element geodynamic code ASPECT.
The first main finding of this work is to suggest that the temporal variability of shortening in the Central Andes is primarily controlled by the subduction dynamics of the Nazca plate while it penetrates into the mantle transition zone. These dynamics depends on the westward velocity of the South American plate that provides the main crustal shortening force to the Andes and forces the trench to retreat. When the subducting plate reaches the lower mantle, it buckles on it-self until the forced trench retreat causes the slab to steepen in the upper mantle in contrast with the classical slab-anchoring model. The steepening of the slab hinders the trench causing it to resist the advancing South American plate, resulting in the pulsatile shortening. This buckling and steepening subduction regime could have been initiated because of the overall decrease in the westwards velocity of the South American plate. In addition, the passage of the flat-slab is required to promote the shortening of the continental plate because flat subduction scrapes the mantle lithosphere, thus weakening the continental plate. This process contributes to the efficient shortening when the trench is hindered, followed by mantle lithosphere delamination at ~20 Ma. Finally, the underthrusting of the Brazilian cratonic shield beneath the orogen occurs at ~11 Ma due to the mechanical weakening of the thick sediments covered the shield margin, and due to the decreasing resistance of the weakened lithosphere of the orogen.
The second main finding of this work is to suggest that the cold flat-slab strengthens the overriding continental lithosphere and prevents strain localization. Therefore, the deformation is transmitted to the eastern front of the flat-slab segment by the shear stress operating at the subduction interface, thus the flat-slab acts like an indenter that “bulldozes” the mantle-keel of the continental lithosphere. The offset in the propagation of deformation to the east between the flat and steeper slab segments in the south causes the formation of a transpressive dextral shear zone. Here, inherited faults of past tectonic events are reactivated and further localize the deformation in an en-echelon strike-slip shear zone, through a mechanism that I refer to as “flat-slab conveyor”. Specifically, the shallowing of the flat-slab causes the lateral deformation, which explains the timing of multiple geological events preceding the arrival of the flat-slab at 33°S. These include the onset of the compression and of the transition between thin to thick-skinned deformation styles resulting from the crustal contraction of the crust in the Sierras Pampeanas some 10 and 6 Myr before the Juan Fernandez Ridge collision at that latitude, respectively.
Late-type stars are by far the most frequent stars in the universe and of fundamental interest to various fields of astronomy – most notably to Galactic archaeology and exoplanet research. However, such stars barely change during their main sequence lifetime; their temperature, luminosity, or chemical composition evolve only very slowly over the course of billions of years. As such, it is difficult to obtain the age of such a star, especially when it is isolated and no other indications (like cluster association) can be used. Gyrochronology offers a way to overcome this problem.
Stars, just like all other objects in the universe, rotate and the rate at which stars rotate impacts many aspects of their appearance and evolution. Gyrochronology leverages the observed rotation rate of a late-type main sequence star and its systematic evolution to estimate their ages. Unlike the above-mentioned parameters, the rotation rate of a main sequence star changes drastically throughout its main sequence lifetime; stars spin down. The youngest stars rotate every few hours, whereas much older stars rotate only about once a month, or – in the case of some late M-stars – once in a hundred days. Given that this spindown is systematic (with an additional mass dependence), it gave rise to the idea of using the observed rotation rate of a star (and its mass or a suitable proxy thereof) to estimate a star’s age. This has been explored widely in young stellar open clusters but remains essentially unconstrained for stars older than the sun, and K and M stars older than 1 Gyr.
This thesis focuses on the continued exploration of the spindown behavior to assess, whether gyrochronology remains applicable for stars of old ages, whether it is universal for late-type main sequence stars (including field stars), and to provide calibration mileposts for spindown models. To accomplish this, I have analyzed data from Kepler space telescope for the open clusters Ruprecht 147 (2.7 Gyr old) and M 67 (4 Gyr). Time series photometry data (light curves)
were obtained for both clusters during Kepler’s K2 mission. However, due to technical limitations and telescope malfunctions, extracting usable data from the K2 mission to identify (especially long) rotation periods requires extensive data preparation.
For Ruprecht 147, I have compiled a list of about 300 cluster members from the literature and adopted preprocessed light curves from the Kepler archive where available. They have been cleaned of the gravest of data artifacts but still contained systematics. After correcting them for said artifacts, I was able to identify rotation periods in 31 of them.
For M 67 more effort was taken. My work on Ruprecht 147 has shown the limitations imposed by the preselection of Kepler targets. Therefore, I adopted the time series full frame image directly and performed photometry on a much higher spatial resolution to be able to obtain data for as many stars as possible. This also means that I had to deal with the ubiquitous artifacts in Kepler data. For that, I devised a method that correlates the artificial flux variations with the ongoing drift of the telescope pointing in order to remove it. This process was a large success and I was able to create light curves whose quality match and even exceede those that were created by the Kepler mission – all while operating on higher spatial resolution and processing fainter stars. Ultimately, I was able to identify signs of periodic variability in the (created) light curves for 31 and 47 stars in Ruprecht 147 and M 67, respectively. My data connect well to bluer stars of cluster of the same age and extend for the first time to stars redder than early-K and older than 1 Gyr. The cluster data show a clear flattening in the distribution of Ruprecht 147 and even a downturn for M 67, resulting in a somewhat sinusoidal shape. With that, I have shown that the systematic spindown of stars continues at least until 4 Gyr and stars continue to live on a single surface in age-rotation periods-mass space which allows gyrochronology to be used at least up to that age. However, the shape of the spindown – as exemplified by the newly discovered sinusoidal shape of the cluster sequence – deviates strongly from the expectations.
I then compiled an extensive sample of rotation data in open clusters – very much including my own work – and used the resulting cluster skeleton (with each cluster forming a rip in color-rotation period-mass space) to investigate if field stars follow the same spindown as cluster stars. For the field stars, I used wide binaries, which – with their shared origin and coevality – are in a sense the smallest possible open clusters. I devised an empirical method to evaluate the consistency between the rotation rates of the wide binary components and found that the vast majority of them are in fact consistent with what is observed in open clusters. This leads me to conclude that gyrochronology – calibrated on open clusters – can be applied to determine the ages of field stars.
Complex emulsions are dispersions of kinetically stabilized multiphasic emulsion droplets comprised of two or more immiscible liquids that provide a novel material platform for the generation of active and dynamic soft materials. In recent years, the intrinsic reconfigurable morphological behavior of complex emulsions, which can be attributed to the unique force equilibrium between the interfacial tensions acting at the various interfaces, has become of fundamental and applied interest. As such, particularly biphasic Janus droplets have been investigated as structural templates for the generation of anisotropic precision objects, dynamic optical elements or as transducers and signal amplifiers in chemo- and bio-sensing applications. In the present thesis, switchable internal morphological responses of complex droplets triggered by stimuli-induced alterations of the balance of interfacial tensions have been explored as a universal building block for the design of multiresponsive, active, and adaptive liquid colloidal systems. A series of underlying principles and mechanisms that influence the equilibrium of interfacial tensions have been uncovered, which allowed the targeted design of emulsion bodies that can alter their shape, bind and roll on surfaces, or change their geometrical shape in response to chemical stimuli. Consequently, combinations of the unique triggerable behavior of Janus droplets with designer surfactants, such as a stimuli-responsive photosurfactant (AzoTAB) resulted for instance in shape-changing soft colloids that exhibited a jellyfish inspired buoyant motion behavior, holding great promise for the design of biological inspired active material architectures and transformable soft robotics.
In situ observations of spherical Janus emulsion droplets using a customized side-view microscopic imaging setup with accompanying pendant dropt measurements disclosed the sensitivity regime of the unique chemical-morphological coupling inside complex emulsions and enabled the recording of calibration curves for the extraction of critical parameters of surfactant effectiveness. The deduced new "responsive drop" method permitted a convenient and cost-efficient quantification and comparison of the critical micelle concentrations (CMCs) and effectiveness of various cationic, anionic, and nonionic surfactants. Moreover, the method allowed insightful characterization of stimuli-responsive surfactants and monitoring of the impact of inorganic salts on the CMC and surfactant effectiveness of ionic and nonionic surfactants. Droplet functionalization with synthetic crown ether surfactants yielded a synthetically minimal material platform capable of autonomous and reversible adaptation to its chemical environment through different supramolecular host-guest recognition events. Addition of metal or ammonium salts resulted in the uptake of the resulting hydrophobic complexes to the hydrocarbon hemisphere, whereas addition of hydrophilic ammonium compounds such as amino acids or polypeptides resulted in supramolecular assemblies at the hydrocarbon-water interface of the droplets. The multiresponsive material platform enabled interfacial complexation and
thus triggered responses of the droplets to a variety of chemical triggers including metal ions, ammonium compounds, amino acids, antibodies, carbohydrates as well as amino-functionalized solid surfaces.
In the final chapter, the first documented optical logic gates and combinatorial logic circuits based on complex emulsions are presented. More specifically, the unique reconfigurable and multiresponsive properties of complex emulsions were exploited to realize droplet-based logic gates of varying complexity using different stimuli-responsive surfactants in combination with diverse readout methods. In summary, different designs for multiresponsive, active, and adaptive liquid colloidal systems were presented and investigated, enabling the design of novel transformative chemo-intelligent soft material platforms.
Technologically important, environmentally friendly InP quantum dots (QDs) typically used as green and red emitters in display devices can achieve exceptional photoluminescence quantum yields (PL QYs) of near-unity (95-100%) when the-state-of-the-art core/shell heterostructure of the ZnSe inner/ZnS outer shell is elaborately applied. Nevertheless, it has only led to a few industrial applications as QD liquid crystal display (QD–LCD) which is applied to blue backlight units, even though QDs has a lot of possibilities that able to realize industrially feasible applications, such as QD light-emitting diodes (QD‒LEDs) and luminescence solar concentrator (LSC), due to their functionalizable characteristics.
Before introducing the main research, the theoretical basis and fundamentals of QDs are described in detail on the basis of the quantum mechanics and experimental synthetic results, where a concept of QD and colloidal QD, a type-I core/shell structure, a transition metal doped semiconductor QDs, the surface chemistry of QD, and their applications (LSC, QD‒LEDs, and EHD jet printing) are sequentially elucidated for better understanding. This doctoral thesis mainly focused on the connectivity between QD materials and QD devices, based on the synthesis of InP QDs that are composed of inorganic core (core/shell heterostructure) and organic shell (surface ligands on the QD surface). In particular, as for the former one (core/shell heterostructure), the ZnCuInS mid-shell as an intermediate layer is newly introduced between a Cu-doped InP core and a ZnS shell for LSC devices. As for the latter one (surface ligands), the ligand effect by 1-octanethiol and chloride ion are investigated for the device stability in QD‒LEDs and the printability of electro-hydrodynamic (EHD) jet printing system, in which this research explores the behavior of surface ligands, based on proton transfer mechanism on the QD surface.
Chapter 3 demonstrates the synthesis of strain-engineered highly emissive Cu:InP/Zn–Cu–In–S (ZCIS)/ZnS core/shell/shell heterostructure QDs via a one-pot approach. When this unconventional combination of a ZCIS/ZnS double shelling scheme is introduced to a series of Cu:InP cores with different sizes, the resulting Cu:InP/ZCIS/ZnS QDs with a tunable near-IR PL range of 694–850 nm yield the highest-ever PL QYs of 71.5–82.4%. These outcomes strongly point to the efficacy of the ZCIS interlayer, which makes the core/shell interfacial strain effectively alleviated, toward high emissivity. The presence of such an intermediate ZCIS layer is further examined by comparative size, structural, and compositional analyses. The end of this chapter briefly introduces the research related to the LSC devices, fabricated from Cu:InP/ZCIS/ZnS QDs, currently in progress.
Chapter 4 mainly deals with ligand effect in 1-octanethiol passivation of InP/ZnSe/ZnS QDs in terms of incomplete surface passivation during synthesis. This chapter demonstrates the lack of anionic carboxylate ligands on the surface of InP/ZnSe/ZnS quantum dots (QDs), where zinc carboxylate ligands can be converted to carboxylic acid or carboxylate ligands via proton transfer by 1-octanethiol. The as-synthesized QDs initially have an under-coordinated vacancy surface, which is passivated by solvent ligands such as ethanol and acetone. Upon exposure of 1-octanethiol to the QD surface, 1-octanthiol effectively induces the surface binding of anionic carboxylate ligands (derived from zinc carboxylate ligands) by proton transfer, which consequently exchanges ethanol and acetone ligands that bound on the incomplete QD surface. The systematic chemical analyses, such as thermogravimetric analysis‒mass spectrometry and proton nuclear magnetic resonance spectroscopy, directly show the interplay of surface ligands, and it associates with QD light-emitting diodes (QD‒LEDs).
Chapter 5 shows the relation between material stability of QDs and device stability of QD‒LEDs through the investigation of surface chemistry and shell thickness. In typical III–V colloidal InP quantum dots (QDs), an inorganic ZnS outermost shell is used to provide stability when overcoated onto the InP core. However, this work presents a faster photo-degradation of InP/ZnSe/ZnS QDs with a thicker ZnS shell than that with a thin ZnS shell when 1-octanethiol was applied as a sulfur source to form ZnS outmost shell. Herein, 1-octanethiol induces the form of weakly-bound carboxylate ligand via proton transfer on the QD surface, resulting in a faster degradation at UV light even though a thicker ZnS shell was formed onto InP/ZnSe QDs. Detailed insight into surface chemistry was obtained from proton nuclear magnetic resonance spectroscopy and thermogravimetric analysis–mass spectrometry. However, the lifetimes of the electroluminescence devices fabricated from InP/ZnSe/ZnS QDs with a thick or a thin ZnS shell show surprisingly the opposite result to the material stability of QDs, where the QD light-emitting diodes (QD‒LEDs) with a thick ZnS shelled QDs maintained its luminance more stable than that with a thin ZnS shelled QDs. This study elucidates the degradation mechanism of the QDs and the QD light-emitting diodes based on the results and discuss why the material stability of QDs is different from the lifetime of QD‒LEDs.
Chapter 6 suggests a method how to improve a printability of EHD jet printing when QD materials are applied to QD ink formulation, where this work introduces the application of GaP mid-shelled InP QDs as a role of surface charge in EHD jet printing technique. In general, GaP intermediate shell has been introduced in III–V colloidal InP quantum dots (QDs) to enhance their thermal stability and quantum efficiency in the case of type-I core/shell/shell heterostructure InP/GaP/ZnSeS QDs. Herein, these highly luminescent InP/GaP/ZnSeS QDs were synthesized and applied to EHD jet printing, by which this study demonstrates that unreacted Ga and Cl ions on the QD surface induce the operating voltage of cone jet and cone jet formation to be reduced and stabilized, respectively. This result indicates GaP intermediate shell not only improves PL QY and thermal stability of InP QDs but also adjusts the critical flow rate required for cone-jet formation. In other words, surface charges of quantum dots can have a significant role in forming cone apex in the EHD capillary nozzle. For an industrially convenient validation of surface charges on the QD surface, Zeta potential analyses of QD solutions as a simple method were performed, as well as inductively coupled plasma optical emission spectrometry (ICP-OES) for a composition of elements.
Beyond the generation of highly emissive InP QDs with narrow FWHM, these studies talk about the connection between QD material and QD devices not only to make it a vital jumping-off point for industrially feasible applications but also to reveal from chemical and physical standpoints the origin that obstructs the improvement of device performance experimentally and theoretically.
Facing the environmental crisis, new technologies are needed to sustain our society. In this context, this thesis aims to describe the properties and applications of carbon-based sustainable materials. In particular, it reports the synthesis and characterization of a wide set of porous carbonaceous materials with high nitrogen content obtained from nucleobases. These materials are used as cathodes for Li-ion capacitors, and a major focus is put on the cathode preparation, highlighting the oxidation resistance of nucleobase-derived materials. Furthermore, their catalytic properties for acid/base and redox reactions are described, pointing to the role of nitrogen speciation on their surfaces. Finally, these materials are used as supports for highly dispersed nickel loading, activating the materials for carbon dioxide electroreduction.
Functional materials, also called "Smart Materials", are described by their ability to fulfill a desired task through targeted interaction with its environment. Due to this functional integration, such materials are of increased interest, especially in areas where the increasing micronization of components is required. Modern manufacturing processes (e.g. microfluidics) and the availability of a wide variety of functional materials (e.g. shape memory materials) now enable the production of particle-based switching components. This category includes micropumps and microvalves, whose basic function is the active control of liquid flows. One approach in realizing those microcomponents as pursued by this work, enables variable size-switching of water-filled microballoons by implementing a stimulus-sensitive switching motif in the capsule's membrane shell, while being under the influence of a constant driving force. The switching motif with its gatekeeper function has a critical influence on one or more material parameters, which modulate the capsule's resistance against the driving force in microballoon expansion process. The advantage of this concept is that even non-variable analyte conditions, such as concentration levels of ions, can be capitalized to generate external force fields that, under the control of the membrane, cause an inflation of the microballoon by an osmotically driven water influx. In case of osmotic pressure gradients as the driving force for the capsule expansion, material parameters associated with the gatekeeper function are specifically the permeability and the mechanical stiffness of the shell material. While a modulation of the shell permeability could be utilized to kinetically impede the water influx on large time scales, a modulation of the shell's mechanical stiffness even might be utilized to completely prevent the capsule inflation due to a possible non-deformability beneath a certain threshold pressure. In polymer networks, which are a suitable material class for the demanded capsule shell because of their excellent elasticity, both the permeability and the mechanical properties are strongly influenced by the crystallinity of the material. Since the permeability is effectively reduced with increasing crystallinity, while the mechanical stiffness is simultaneously greatly increased, both effects point in the same direction in terms of their functional relationship. For this reason and due to a reversible and contactless modulation of the membrane crystallinity by heat input, crystallites may be suitable switching motifs for controlling the capsule expansion. As second design element of reversible expandable microballoons, the capsule geometry, defined by an aqueous core enveloped by the temperature-sensitive polymer network membrane, should allow an osmotic pressure gradient across the membrane layer. The strength of the inflation pressure and the associated inflation velocity upon membrane melting should be controlled by the salt concentration within the aqueous core, while a turn in the osmotic gradient should furthermore allow the reversible process of capsule deflation. Therefore, it should be possible to build either microvalves and micropumps, while their intended action of either pumping or valving is determined by their state of expansion and the direction of the osmotic pressure gradient.. Microballoons of approximately 300 µm in diameter were formed via droplet-based microfluidics from double-emulsion templates (w/o/w). The elastomeric capsule membrane was formed by photo-crosslinking of methacrylate (MA) functionalized oligo(ε-caprolactone) precursors (≈ 3.8 MA-arms, Mn ≈ 12000 g mol-1) within the organic medium layer (o) via UV-exposure after droplet-formation. After removal of the toluene/chloroform mixture by slow extraction via the continuous aqueous phase, the capsules solidified under the development of a characteristic "mushroom"-like shape at specific experimental conditions (e.g. λ = 308 nm, 57 mJ·s-1·cm-2, 16 min). It could be furthermore shown that in dependency to the process parameters: oligomer concentration and curing-time also spherical capsules were accessible. Long curing-times and high oligomer concentrations at a fixed light-intensity favored the formation of "mushroom"-like capsules, whereas the contrary led to spherical shaped capsules. A comparative study on thin polymer network films of same composition and equal treatment proved a correlation between the film's crosslink density and their contraction capability, while stronger crosslinked polymer networks showed a stronger contraction after solvent removal. In combination with observations during capsule solidification via light-microscopy, where a continuous shaping from almost spherical crosslinked templates to "mushroom"-shaped and solidified capsules was stated, the following mechanism was proposed. In case of low oligomer contents and short curing-times, the contraction of the capsule shell during solvent removal is strongly diminished due to a low degree of crosslinking. Therefore, the solidifying shell could freely collapse onto the aqueous core. In the other case, high oligomer concentrations and long curing-times will favor the formation of highly crosslinked capsule membranes with a strong contraction capability. Due to an observed decentered location of the aqueous core within the swollen polymer network, an uneven radial stress along the capsule's circumference is exerted to the incompressible core. This lead to an uneven contraction during solvent removal and a directed flow of the core fluid into the direction of the minimal stress vector. In consequence, the initially thicker spherical cap contracts, whereas the opposing thinner spherical cap get stretched. The "mushroom"-shape over some advantages over their spherical shaped counterparts, why they were selected for the further experiments. Besides the necessity of a high density of crosslinking for the purpose of extraordinary elasticity and toughness, the form-anisotropy promotes a faster microballoon expandability due to a partial reduction of the membrane thickness. Additionally, pre-stretched regions of thin thickness might provide a better resistance against inflation pressure than spherical but non-stretched capsules of equal membrane thickness. The resulting "mushroom"-shaped microcapsules exhibited a melting point of Tm ≈ 50 - 60 °C and a degree of crystallinity of Xc ≈ 29 - 38 % depending on the membrane thickness and internal salt content, which is slightly lower than for the non-crosslinked oligomer and reasoned by a limited chain mobility upon crosslinking. Nonetheless, the melting transition of the polymer network was associated with a strong drop in its mechanical stiffness, which was shown to have a strong influence on the osmotic driven expansion of the microcapsules. Capsules that were subjected to osmotic pressures between 1.5 and 4.7 MPa did not expand if the temperature was well below the melting point of the capsule's membrane, i.e. at room temperature. In contrast, a continuous expansion, while approaching asymptotically to a final capsule size, was observed if the temperature exceeded the melting point, i.e. 60 °C. Microballoons, which were kept for 56 days at ∆Π = 1.5 MPa and room temperature, did not change significantly in diameter, why the impact of the mechanical stiffness on the expansion behavior is considered to be the greater than the influence of the shell permeability. The time-resolved expansion behavior of the microballoons above their Tm was subsequently modeled, using difusion equations that were corrected for shape anisotropy and elastic restoring forces. A shape-related and expansion dependent pre-factor was used to dynamically address the influence of the shell thickness differences along the circumference on the inflation velocity, whereas the microballoon's elastic contraction upon inflation was rendered by the inclusion of a hyperelastic constitutive model. An important finding resulting from this model was the pronounced increase in inflation velocity compared to hypothetical capsules with a homogeneous shell thickness, which stresses the benefit of employing shape anisotropic balloon-like capsules in this study. Furthermore, the model was able to predict the finite expandability on basis of entropy-elastic recovery forces and strain-hardening effects. A comparison of six different microballoons with different shell thicknesses and internal salt contents showed the linear relationship between the volumetric expansion, the shell thickness and the applied osmotic pressure, as represented by the model. As the proposed model facilitates the prediction of the expansion kinetics depending on the membranes mechanical and diffusional characteristics, it might be a screening tool for future material selections. In course of the microballoon expansion process, capsules of intermediate diameters could be isolated by recrystallization of the membrane, which is mainly caused by a restoration of the membrane's mechanical stiffness and is otherwise difficult to achieve with other stimuli-sensitive systems. The capsule's crystallinity of intermediate expansion states was nearly unchanged, whereas the lamellar crystal size tends to decreased with the expansion ratio. Therefore, it was assumed that the elastic modulus was only minimally altered and might increased due to the networks segment-chain extension. In addition to the volume increase achieved by inflation, a turn in the osmotic gradient also facilitated the reversible deflation, which was shown in inflation/deflation cycles. These both characteristics of the introduced microballoons are important parameter regarding the realization of micropumps and microvalves. The fixation of expanded microcapsules via recrystallization enabled the storage of entropy-elastic strain-energy, which could be utilized for pumping actions in non-aqueous media. Here, the pumping velocity depended on both, the type of surrounding medium and the applied temperature. Surrounding media that supported the fast transport of pumped liquid showed an accelerated deflation, while high temperatures further accelerate the pumping velocity. Very fast rejection of the incorporated payload was furthermore realized with pierced expanded microballoons, which were subjected to temperatures above their Tm. The possible fixation of intermediate particle sizes provide opportunities for vent constructions that allowed the precise adjustment of specific flow-rates and multiple valve openings and closings. A valve construction was realized by the insertion of a single or multiple microballoons in a microfluidic channel. A complete and a partial closing of the microballoon-valves was demonstrated as a function of the heating period. In this context, a difference between the inflation and deflation velocity was stated, summarizing slower expansion kinetics. Overall, microballoons, which presented both on-demand pumping and reversible valving by a temperature-triggered change in the capsule's volume, might be suitable components that help to design fully integrated LOC devices, due to the implementation of the control switch and controllable inflation/deflation kinetics. In comparison to other state of the art stimuli-sensitive materials, one has to highlight the microballoons capability of stabilizing almost continuously intermediate capsule sizes by simple recrystallization of the microballoon's membrane.
Diversity is a term that is broadly used and challenging for informatics research, development and education. Diversity concerns may relate to unequal participation, knowledge and methodology, curricula, institutional planning etc. For a lot of these areas, measures, guidelines and best practices on diversity awareness exist. A systemic, sustainable impact of diversity measures on informatics is still largely missing. In this paper I explore what working with diversity and gender concepts in informatics entails, what the main challenges are and provide thoughts for improvement. The paper includes definitions of diversity and intersectionality, reflections on the disciplinary basis of informatics and practical implications of integrating diversity in informatics research and development. In the final part, two concepts from the social sciences and the humanities, the notion of “third space”/hybridity and the notion of “feminist ethics of care”, serve as a lens to foster more sustainable ways of working with diversity in informatics.
Ethical issues surrounding modern computing technologies play an increasingly important role in the public debate. Yet, ethics still either doesn’t appear at all or only to a very small extent in computer science degree programs. This paper provides an argument for the value of ethics beyond a pure responsibility perspective and describes the positive value of ethical debate for future computer scientists. It also provides a systematic analysis of the module handbooks of 67 German universities and shows that there is indeed a lack of ethics in computer science education. Finally, we present a principled design of a compulsory course for undergraduate students.
While inequality of opportunity (IOp) in earnings is well studied, the literature on IOp in individual net wealth is scarce to non-existent. This is problematic because both theoretical and empirical evidence show that the position in the wealth and income distribution can significantly diverge.We measure ex-ante IOp in net wealth for Germany using data from the Socio-Economic Panel (SOEP). Ex-ante IOp is defined as the contribution of circumstances to the inequality in net wealth before effort is exerted. The SOEP allows for a direct mapping from individual circumstances to individual net wealth and for a detailed decomposition of net wealth inequality into a variety of circumstances; among them childhood background, intergenerational transfers, and regional characteristics. The ratio of inequality of opportunity to total inequality is stable from 2002 to 2019. This is in sharp contrast to labor earnings, where ex-ante IOp is declining over time. Our estimates suggest that about 62% of the inequality in net wealth is due to circumstances. The most important circumstances are intergenerational transfers, parental occupation, and the region of birth. In contrast, gender and individuals’ own education are the most important circumstances for earnings.
High growth firms (HGFs) are important for job creation and considered to be precursors of economic growth. We investigate how formal institutions, like product- and labor-market regulations, as well as the quality of regional governments that implement these regulations, affect HGF development across European regions. Using data from Eurostat, OECD, WEF, and Gothenburg University, we show that both regulatory stringency and the quality of the regional government influence the regional shares of HGFs. More importantly, we find that the effect of labor- and product-market regulations ultimately depends on the quality of regional governments: in regions with high quality of government, the share of HGFs is neither affected by the level of product market regulation, nor by more or less flexibility in hiring and firing practices. Our findings contribute to the debate on the effects of regulations by showing that regulations are not, per se, “good, bad, and ugly”, rather their impact depends on the efficiency of regional governments. Our paper offers important building blocks to develop tailored policy measures that may influence the development of HGFs in a region.
In the past decades, scholars and courts have paid considerable attention to the extraterritorial applicability of human rights treaties. By contrast, the extraterritorial application of constitutional rights has received comparable scholarly attention only in the United States. Specifically, there is a paucity of comparative research in this area, which contributes to the prevailing view that human rights law provides the proper framework under which domestic courts should examine extraterritoriality questions under constitutional law.
This article argues that domestic constitutional regimes and their judicial enforcers can and should provide an important counterweight to the deadlocked extraterritoriality debate at the international level. Using two case studies from Germany and the United States, it shows that domestic constitutional courts are sometimes better suited than treaty bodies to guard the normative values of human dignity and universality in an extraterritoriality context. This is most apparent in the case of Germany, which has a long tradition of integration into international multi-level governance systems and "bottom-up" resistance based on fundamental rights within such systems. Recent cases from the Federal Constitutional Court (Bundesverfassungsgericht) about the extraterritorial application of the Basic Law (Grundgesetz) to foreign intelligence gathering and climate change support this theory. However, an independent constitutional approach can also achieve some normative effects in domestic systems that are more isolated from the international human rights system. Thus, the US Supreme Court likewise used domestic constitutional doctrine to sidestep the American government's strictly territorial interpretation of the ICCPR and employ a functional approach to the extraterritorial applicability of fundamental rights in the case of detention of suspected terrorists in the Guantánamo Bay naval base.
The study of these two examples does not purport to be comprehensive or even representative of the world’s diverse array of constitutions and their relationships with international human rights law. However, the independent power of constitutional frameworks in these two disparate cases should all the more provide an impetus for increased comparative research into constitutional extraterritoriality regimes and their value for the project of human rights.
Supporting reflection in preservice during university-based training is, without doubt, a crucial aspect in attaining teacher professionalism. Therefore, an on-campus seminar designed to relate theory to practice and vice versa – the so-called ‘Lehr-Lern-Labor-Seminar (LLLS)’ – was implemented over the course of five terms to stimulate reflective skills of English and Physics teacher trainees. Investigations on the effectiveness of three types of the LLLS (no video and two types of video-supported reflections) compared to a parallel group (PG) and a control group (CG) occurred in a mixed methods quasi-experimental study. Reflective skills were elicited with vignettes, relevant covariates with questionnaires. Reflective development was then traced in the dimensions depth and breadth employing a qualitative content analysis. MANCOVA (Multivariate Analysis of Covariance) and regression analyses revealed a substantive increase of reflective depth for English and Physics teacher trainees and breadth development for English LLLS-participants in contrast to both, a PG and a CG, even when controlling for the subjects’ individual prerequisites.
Carbon dioxide removal from the atmosphere is becoming an important option to achieve net zero climate targets. This paper develops a welfare and public economics perspective on optimal policies for carbon removal and storage in non-permanent sinks like forests, soil, oceans, wood products or chemical products. We derive a new metric for the valuation of non-permanent carbon storage, the social cost of carbon removal (SCC-R), which embeds also the conventional social cost of carbon emissions. We show that the contribution of CDR is to create new carbon sinks that should be used to reduce transition costs, even if the stored carbon is released to the atmosphere eventually. Importantly, CDR does not raise the ambition of optimal temperature levels unless initial atmospheric carbon stocks are excessively high. For high initial atmospheric carbon stocks, CDR allows to reduce the optimal temperature below initial levels. Finally, we characterize three different policy regimes that ensure an optimal deployment of carbon removal: downstream carbon pricing, upstream carbon pricing, and carbon storage pricing. The policy regimes differ in their informational and institutional requirements regarding monitoring, liability and financing.
National Action Plans (NAPs) have been increas-ingly adopted world-wide after the Vienna Dec-laration in 1993, where it was urged to consider the improvement and promotion of Human Rights. In this paper, we discuss their usefulness and success by analysing the challenges present-ed during NAP processes as well as the benefits this set of actions entails: The challenges for their implementation outweigh its actual benefits. Nevertheless, NAPs have great potential. Based on new research, we elaborate a set of recom-mendations for improving the design and imple-mentation of national action planning. In order to effectively bring NAP into practice, we consider it crucial to plan and analyse every state local circumstances in detail. The latter is important, since the implementation of a concrete set of actions is intended to directly transform and improve the local living conditions of the people. In a long-term perspective, we defend the benefit of NAP’s implementation for complying obliga-tions set up by HR treaties.
The last years have been affected by Covid-19 and the international emergency mecha-nism to deal with health-related threats. The effects of this period manifested differ-ently worldwide, depending on matters such as international relations, national policies, power dynamics etc. Additionally, the impact of this time will likely have long-term effects which are yet to be known. This paper gives a critical overview of the Public Health Emergency of International Concern (PHEIC) mechanism in the context of Covid-19. It does so by explaining the legal framework for states of emergency, specifically in the context of a PHEIC, while considering its restrictions and limitations on human rights. It further outlines issues in the manifestation of global protections and limitations on human rights during Covid-19. Lastly, considering the likelihood of future PHEICs and the known systemic obstructions, this paper offers ways to im-prove this mechanism from a holistic, non-zero-sum perspective.
A degree course in IT and business administration solely for women (FIW) has been offered since 2009 at the HTW Berlin – University of Applied Sciences. This contribution discusses student motivations for enrolling in such a women only degree course and gives details of our experience over recent years. In particular, the approach to attracting new female students is described and the composition of the intake is discussed. It is shown that the women-only setting together with other factors can attract a new clientele for computer science.
Recent research suggests that design thinking practices may foster the development of needed capabilities in new digitalised landscapes. However, existing publications represent individual contributions, and we lack a holistic understanding of the value of design thinking in a digital world. No review, to date, has offered a holistic retrospection of this research. In response, in this bibliometric review, we aim to shed light on the intellectual structure of multidisciplinary design thinking literature related to capabilities relevant to the digital world in higher education and business settings, highlight current trends and suggest further studies to advance theoretical and empirical underpinnings. Our study addresses this aim using bibliometric methods—bibliographic coupling and co-word analysis as they are particularly suitable for identifying current trends and future research priorities at the forefront of the research. Overall, bibliometric analyses of the publications dealing with the related topics published in the last 10 years (extracted from the Web of Science database) expose six trends and two possible future research developments highlighting the expanding scope of the design thinking scientific field related to capabilities required for the (more sustainable and human-centric) digital world. Relatedly, design thinking becomes a relevant approach to be included in higher education curricula and human resources training to prepare students and workers for the changing work demands. This paper is well-suited for education and business practitioners seeking to embed design thinking capabilities in their curricula and for design thinking and other scholars wanting to understand the field and possible directions for future research.
Desperados at Sea
(2023)
Pirates are fortune-seeking fighters at sea. Their exploits fire the imaginations of their victims and admirers, drawing a veil over individuals who rarely bear a real name and pursue their adventurous occupations as buccaneers, filibusters, freebooters, privateers, pirates, or corsairs. Piracy, corsairing, and contraband trade were epidemic among the Egyptians and the Phoenicians, the Greeks and the Vikings, the Spaniards and the Ottomans, the Muslims, and the Christians. And the Jews.
“Israel am Meere”
(2023)
For Jews in Germany, the period following the Nazis’ rise to power in January 1933 was a period of decision-making on many levels: How should they respond to the persecution? If they decided to emigrate, many more decisions had to be made: How does one leave a country, and where should one go? A key moment in the process and in the cultural practice of emigration is the beginning of the sea voyage – when the need for departure and the hope for a new arrival jointly create a period of liminality. Looking at reports from sea voyages of exploration and emigration from the 1930s, this contribution discusses the question whether, and in what ways, such reflections can be read in the context of religious experiences and in the search for Jewish identities in times of turmoil.
“Creating a Maritime Future”
(2023)
This article explores the importance of the port city of Hamburg in the evolving discourses on the creation of a maritime future, a vision which became influential in the 1930s, 1940s and 1950s. While some Jewish representatives in the city aimed at preserving and intertwining Hanseatic and Jewish traditions in order to secure a Jewish presence in the port city under the pressure of the Nazi regime and thereafter, others wanted to create new emigration opportunities, especially to Mandatory Palestine, and create a Jewish maritime future in Eretz Israel. Different Zionist organizations supported the newly evolving maritime ideas, such as the “conquest of the sea”, and promoted the image of a Jewish seafaring nation. Despite the difficulties in the 1940s, these concepts gained influence post-1945 and led to the foundation of the fishery kibbutz “Zerubavel” in Blankenese/Hamburg. However, the idea of a Hanseatic Jewish future also remained influential and illustrates how differently a “Jewish maritime future” was imagined and used to link past, present and future.
Jacob Brandon Maduro’s Memoirs and Related Observations (Havana, 1953) speak to the lasting yet malleable legacy of Jewish Caribbean/Atlantic mercantile communities that defined early modern settlement in the Americas. A close reading of the Memoirs, alongside relevant archival records and community narratives, lends new perspectives to scholarship on Port Jewries and the Atlantic Diaspora. Specifically concerned with Jacob’s adoption of such leading intellectual and political tropes as the Monroe doctrine, José Martí’s Nuestra America, and a Zionism that evolved from an ideology to a reality, the Memoirs reveal a narrative at once defined by the tremendous upheavals of the first half of the 20th century, and an enduring sense of Jewish diasporic peoplehood defined through a Port Jew paradigm whereby the preservation of Jewish ethnicity is understood as synonymous with the championing of modernity.
Twenty-four scientists met for the annual Auxological conference held at Krobielowice castle, Poland, to discuss the diverse influences of the environment and of social behavior on growth following last year’s focus on growth and public health concerns (Hermanussen et al., 2022b). Growth and final body size exhibit marked plastic responses to ecological conditions. Among the shortest are the pygmoid people of Rampasasa, Flores, Indonesia, who still live under most secluded insular conditions. Genetics and nutrition are usually considered responsible for the poor growth in many parts of this world, but evidence is accumulating on the prominent impact of social embedding on child growth. Secular trends not only in the growth of height, but also in body proportions, accompany the secular changes in the social, economic and political conditions, with major influences on the emotional and educational circumstances under which the children grow up (Bogin, 2021). Aspects of developmental tempo and aspects of sports were discussed, and the impact of migration by the example of women from Bangladesh who grew up in the UK. Child growth was considered in particular from the point of view of strategic adjustments of individual size within the network of its social group. Theoretical considerations on network characteristics were presented and related to the evolutionary conservation of growth regulating hypothalamic neuropeptides that have been shown to link behavior and physical growth in the vertebrate species. New statistical approaches were presented for the evaluation of short term growth measurements that permit monitoring child growth at intervals of a few days and weeks.
Background: Assessing short-term growth in humans is still fraught with difficulties. Especially when looking for small variations and increments, such as mini growth spurts, high precision instruments or frequent measurements are necessary. Daily measurements however require a lot of effort, both for anthropologists and for the subjects. Therefore, new sophisticated approaches are needed that reduce fluctuations and reveal underlying patterns.
Objectives: Changepoints are abrupt variations in the properties of time series data. In the context of growth, such variations could be variation in mean height. By adjusting the variance and using different growth models, we assessed the ability of changepoint analysis to analyse short-term growth and detect mini growth spurts.
Sample and Methods: We performed Bayesian changepoint analysis on simulated growth data using the bcp package in R. Simulated growth patterns included stasis, linear growth, catch-up growth, and mini growth spurts. Specificity and a normalised variant of the Matthews correlation coefficient (MCC) were used to assess the algorithm’s performance. Welch’s t-test was used to compare differences of the mean.
Results: First results show that changepoint analysis can detect mini growth spurts. However, the ability to detect mini growth spurts is highly dependent on measurement error. Data preparation, such as ranking and rotating time series data, showed negligible improvements. Missing data was an issue and may affect the prediction quality of the classification metrics.
Conclusion: Changepoint analysis is a promising tool to analyse short-term growth. However, further optimisation and analysis of real growth data is needed to make broader generalisations.
Human growth data analysis and statistics – the 5th Gülpe International Student Summer School
(2023)
The Summer School in Gülpe (Ecological Station of the University of Potsdam) offers an exceptional learning opportunity for students to apply their knowledge and skills to real-world problems. With the guidance of experienced human biologists, statisticians, and programmers, students have the unique chance to analyze their own data and gain valuable insights. This interdisciplinary setting not only bridges different research areas but also leads to highly valuable outputs. The progress of students within just a few days is truly remarkable, especially when they are motivated and receive immediate feedback on their questions, problems, and results. The Summer School covers a wide range of topics, with this year’s focus mainly on two areas: understanding the impact of socioeconomic and physiological factors on human development and mastering statistical techniques for analyzing data such as changepoint analysis and the St. Nicolas House Analysis (SNHA) to visualize interacting variables. The latter technique, born out of the Summer School’s emphasis on gaining comprehensive data insights and understanding major relationships, has proven to be a valuable tool for researchers in the field. The articles in this special issue demonstrate that the Summer School in Gülpe stands as a testament to the power of practical learning and collaboration. Students who attend not only gain hands-on experience but also benefit from the expertise of professionals and the opportunity to engage with peers from diverse disciplines.
No evidence of growth impairment after forced migration in Polish school children after World War II
(2023)
Background: Migration is omnipresent. It can come hand in hand with emotional stress which is known to influence the growth of children.
Objective: The aim of this study was to analyse whether type of migration (forced or voluntary) and the geographic direction had influenced the growth of Polish children after World War II.
Sample and Methods: A sub dataset of 2,208 individuals between the ages of 2-20, created from data of the 2nd Polish Anthropological Survey carried out in 1966–1969, including anthropometrical data and social and demographic information based on questionnaire, was used to analyse migration effects.
Results: No association could be found between the direction of migration and the height of the children. The confidence intervals of the means of all classified migration categories overlap significantly and the effect size of the influence of migration category on height is ds=.140, which is too low to see any effects, even if there were one.
Conclusion: Neither forced nor voluntary migration in Poland after World War II led to a change in height in children of migrating families.
Nutrition, size, and tempo
(2023)
Nutrition is a prerequisite, but not a regulator of growth. Growth is defined as increase in size over time. The understanding of growth includes an understanding of the binary concept of physical time and individual tempo. Excess food causes tempo acceleration. Food restriction delays tempo. Tempo reflects the pace of life. It is a dynamic physical response to a broad spectrum of social, economic, political, and emotional (SEPE) factors and can affect life expectancy. Variations in tempo create distortions of the z-score patterns of height and weight. Illness or intermediate food shortage lead to intermediate halts in development and create short dips in the z-score patterns. Children who develop throughout life at delayed pace usually run at lower z-scores for height and weight, and show a characteristic adolescent trough; children who develop throughout life at faster than average pace usually run at higher z-scores and show a characteristic adolescent peak in their z-score patterns. During adolescence, almost half of the height variance is due to tempo variation. There is not one tempo for the whole body. Different organ systems grow and mature at different pace.
What does stunting tell us?
(2023)
Stunting is commonly linked with undernutrition. Yet, already after World War I, German pediatricians questioned this link and stated that no association exists between nutrition and height. Recent analyses within different populations of Low- and middle-income countries with high rates of stunted children failed to support the assumption that stunted children have a low BMI and skinfold sickness as signs of severe caloric deficiency. So, stunting is not a synonym of malnutrition. Parental education level has a positive influence on body height in stunted populations, e.g., in India and in Indonesia. Socially disadvantaged children tend to be shorter and lighter than children from affluent families.
Humans are social mammals; they regulate growth similar to other social mammals. Also in humans, body height is strongly associated with the position within the social hierarchy, reflecting the personal and group-specific social, economic, political, and emotional environment. These non-nutritional impact factors on growth are summarized by the concept of SEPE (Social-Economic-Political-Emotional) factors. SEPE reflects on prestige, dominance-subordination, social identity, and ego motivation of individuals and social groups.
Under Brazil's ex-president Bolsonaro, deforestation of the Amazon increased dramatically. An Austrian NGO filed a complaint to the Prosecutor of the International Criminal Court (ICC) against Bolsonaro in October 2021, accusing him of crimes against humanity against the backdrop of his involvement in environmental destruction. This paper deals with the question of whether this initi-ative constitutes a promising means of juridification to mitigate conflicts revolving around mass deforestation in Brazil. It thematizes attempts to juridify environmental destruction in international criminal law and examines the Climate Fund Case at the Brazilian Supreme Court. Finally, emerging problems and arguments in favour of starting preliminary examinations at the ICC against Bolsonaro are illuminated. This paper provides arguments as to why the initiative might be a promising undertaking, even though it is unlikely that Bolsonaro will be arrested.
Earthquake modeling is the key to a profound understanding of a rupture. Its kinematics or dynamics are derived from advanced rupture models that allow, for example, to reconstruct the direction and velocity of the rupture front or the evolving slip distribution behind the rupture front. Such models are often parameterized by a lattice of interacting sub-faults with many degrees of freedom, where, for example, the time history of the slip and rake on each sub-fault are inverted. To avoid overfitting or other numerical instabilities during a finite-fault estimation, most models are stabilized by geometric rather than physical constraints such as smoothing.
As a basis for the inversion approach of this study, we build on a new pseudo-dynamic rupture model (PDR) with only a few free parameters and a simple geometry as a physics-based solution of an earthquake rupture. The PDR derives the instantaneous slip from a given stress drop on the fault plane, with boundary conditions on the developing crack surface guaranteed at all times via a boundary element approach. As a side product, the source time function on each point on the rupture plane is not constraint and develops by itself without additional parametrization. The code was made publicly available as part of the Pyrocko and Grond Python packages. The approach was compared with conventional modeling for different earthquakes. For example, for the Mw 7.1 2016 Kumamoto, Japan, earthquake, the effects of geometric changes in the rupture surface on the slip and slip rate distributions could be reproduced by simply projecting stress vectors. For the Mw 7.5 2018 Palu, Indonesia, strike-slip earthquake, we also modelled rupture propagation using the 2D Eikonal equation and assuming a linear relationship between rupture and shear wave velocity. This allowed us to give a deeper and faster propagating rupture front and the resulting upward refraction as a new possible explanation for the apparent supershear observed at the Earth's surface.
The thesis investigates three aspects of earthquake inversion using PDR: (1) to test whether implementing a simplified rupture model with few parameters into a probabilistic Bayesian scheme without constraining geometric parameters is feasible, and whether this leads to fast and robust results that can be used for subsequent fast information systems (e.g., ground motion predictions). (2) To investigate whether combining broadband and strong-motion seismic records together with near-field ground deformation data improves the reliability of estimated rupture models in a Bayesian inversion. (3) To investigate whether a complex rupture can be represented by the inversion of multiple PDR sources and for what type of earthquakes this is recommended.
I developed the PDR inversion approach and applied the joint data inversions to two seismic sequences in different tectonic settings. Using multiple frequency bands and a multiple source inversion approach, I captured the multi-modal behaviour of the Mw 8.2 2021 South Sandwich subduction earthquake with a large, curved and slow rupturing shallow earthquake bounded by two faster and deeper smaller events. I could cross-validate the results with other methods, i.e., P-wave energy back-projection, a clustering analysis of aftershocks and a simple tsunami forward model.
The joint analysis of ground deformation and seismic data within a multiple source inversion also shed light on an earthquake triplet, which occurred in July 2022 in SE Iran. From the inversion and aftershock relocalization, I found indications for a vertical separation between the shallower mainshocks within the sedimentary cover and deeper aftershocks at the sediment-basement interface. The vertical offset could be caused by the ductile response of the evident salt layer to stress perturbations from the mainshocks.
The applications highlight the versatility of the simple PDR in probabilistic seismic source inversion capturing features of rather different, complex earthquakes. Limitations, as the evident focus on the major slip patches of the rupture are discussed as well as differences to other finite fault modeling methods.
Solar photocatalysis is the one of leading concepts of research in the current paradigm of sustainable chemical industry. For actual practical implementation of sunlight-driven catalytic processes in organic synthesis, a cheap, efficient, versatile and robust heterogeneous catalyst is necessary. Carbon nitrides are a class of organic semiconductors who are known to fulfill these requirements.
First, current state of solar photocatalysis in economy, industry and lab research is overviewed, outlining EU project funding, prospective synthetic and reforming bulk processes, small scale solar organic chemistry, and existing reactor designs and prototypes, concluding feasibility of the approach.
Then, the photocatalytic aerobic cleavage of oximes to corresponding aldehydes and ketones by anionic poly(heptazine imide) carbon nitride is discussed. The reaction provides a feasible method of deprotection and formation of carbonyl compounds from nitrosation products and serves as a convenient model to study chromoselectivity and photophysics of energy transfer in heterogeneous photocatalysis.
Afterwards, the ability of mesoporous graphitic carbon nitride to conduct proton-coupled electron transfer was utilized for the direct oxygenation of 1,3-oxazolidin-2-ones to corresponding 1,3-oxazlidine-2,4-diones. This reaction provides an easier access to a key scaffold of diverse types of drugs and agrochemicals.
Finally, a series of novel carbon nitrides based on poly(triazine imide) and poly(heptazine imide) structure was synthesized from cyanamide and potassium rhodizonate. These catalysts demonstrated a good performance in a set of photocatalytic benchmark reactions, including aerobic oxidation, dual nickel photoredox catalysis, hydrogen peroxide evolution and chromoselective transformation of organosulfur precursors.
Concluding, the scope of carbon nitride utilization for net-oxidative and net-neutral photocatalytic processes was expanded, and a new tunable platform for catalyst synthesis was discovered.
Reactive eutectic media based on ammonium formate for the valorization of bio-sourced materials
(2023)
In the last several decades eutectic mixtures of different compositions were successfully used as solvents for vast amount of chemical processes, and only relatively recently they were discovered to be widely spread in nature. As such they are discussed as a third liquid media of the living cell, that is composed of common cell metabolites. Such media may also incorporate water as a eutectic component in order to regulate properties such as enzyme activity or viscosity. Taking inspiration form such sophisticated use of eutectic mixtures, this thesis will explore the use of reactive eutectic media (REM) for organic synthesis. Such unconventional media are characterized by the reactivity of their components, which means that mixture may assume the role of the solvent as well as the reactant itself.
The thesis focuses on novel REM based on ammonium formate and investigates their potential for the valorization of bio-sourced materials. The use of REM allows the performance of a number of solvent-free reactions, which entails the benefits of a superior atom and energy economy, higher yields and faster rates compared to reactions in solution. This is evident for the Maillard reaction between ammonium formate and various monosaccharides for the synthesis of substituted pyrazines as well as for a Leuckart type reaction between ammonium formate and levulinic acid for the synthesis of 5-methyl-2-pyrrolidone. Furthermore, reaction of ammonium formate with citric acid for the synthesis of yet undiscovered fluorophores, shows that synthesis in REM can open up unexpected reaction pathways.
Another focus of the thesis is the study of water as a third component in the REM. As a result, the concept of two different dilution regimes (tertiary REM and in REM in solvent) appears useful for understanding the influence of water. It is shown that small amounts of water can be of great benefit for the reaction, by reducing viscosity and at the same time increasing reaction yields.
REM based on ammonium formate and organic acids are employed for lignocellulosic biomass treatment. The thesis thereby introduces an alternative approach towards lignocellulosic biomass fractionation that promises a considerable process intensification by the simultaneous generation of cellulose and lignin as well as the production of value-added chemicals from REM components. The thesis investigates the generated cellulose and the pathway to nanocellulose generation and also includes the structural analysis of extracted lignin.
Finally, the thesis investigates the potential of microwave heating to run chemical reactions in REM and describes the synergy between these two approaches. Microwave heating for chemical reactions and the use of eutectic mixtures as alternative reaction media are two research fields that are often described in the scope of green chemistry. The thesis will therefore also contain a closer inspection of this terminology and its greater goal of sustainability.
The Lyman-𝛼 (Ly𝛼) line commonly assists in the detection of high-redshift galaxies, the so-called Lyman-alpha emitters (LAEs). LAEs are useful tools to study the baryonic matter distribution of the high-redshift universe. Exploring their spatial distribution not only reveals the large-scale structure of the universe at early epochs, but it also provides an insight into the early formation and evolution of the galaxies we observe today. Because dark matter halos (DMHs) serve as sites of galaxy formation, the LAE distribution also traces that of the underlying dark matter. However, the details of this relation and their co-evolution over time remain unclear. Moreover, theoretical studies predict that the spatial distribution of LAEs also impacts their own circumgalactic medium (CGM) by influencing their extended Ly𝛼 gaseous halos (LAHs), whose origin is still under investigation. In this thesis, I make several contributions to improve the knowledge on these fields using samples of LAEs observed with the Multi Unit Spectroscopic Explorer (MUSE) at redshifts of 3 < 𝑧 < 6.
Intuitively, strongly constraining contexts should lead to stronger probabilistic representations of sentences in memory. Encountering unexpected words could therefore be expected to trigger costlier shifts in these representations than expected words. However, psycholinguistic measures commonly used to study probabilistic processing, such as the N400 event-related potential (ERP) component, are sensitive to word predictability but not to contextual constraint. Some research suggests that constraint-related processing cost may be measurable via an ERP positivity following the N400, known as the anterior post-N400 positivity (PNP). The PNP is argued to reflect update of a sentence representation and to be distinct from the posterior P600, which reflects conflict detection and reanalysis. However, constraint-related PNP findings are inconsistent. We sought to conceptually replicate Federmeier et al. (2007) and Kuperberg et al. (2020), who observed that the PNP, but not the N400 or the P600, was affected by constraint at unexpected but plausible words. Using a pre-registered design and statistical approach maximising power, we demonstrated a dissociated effect of predictability and constraint: strong evidence for predictability but not constraint in the N400 window, and strong evidence for constraint but not predictability in the later window. However, the constraint effect was consistent with a P600 and not a PNP, suggesting increased conflict between a strong representation and unexpected input rather than greater update of the representation. We conclude that either a simple strong/weak constraint design is not always sufficient to elicit the PNP, or that previous PNP constraint findings could be an artifact of smaller sample size.
Achilles tendinopathy (AT) is a debilitating injury in athletes, especially for those engaged in repetitive stretch-shortening cycle activities. Clinical risk factors are numerous, but it has been suggested that altered biomechanics might be associated with AT. No systematic review has been conducted investigating these biomechanical alterations in specifically athletic populations. Therefore, the aim of this systematic review was to compare the lower-limb biomechanics of athletes with AT to athletically matched asymptomatic controls. Databases were searched for relevant studies investigating biomechanics during gait activities and other motor tasks such as hopping, isolated strength tasks, and reflex responses. Inclusion criteria for studies were an AT diagnosis in at least one group, cross-sectional or prospective data, at least one outcome comparing biomechanical data between an AT and healthy group, and athletic populations. Studies were excluded if patients had Achilles tendon rupture/surgery, participants reported injuries other than AT, and when only within-subject data was available.. Effect sizes (Cohen's d) with 95% confidence intervals were calculated for relevant outcomes. The initial search yielded 4,442 studies. After screening, twenty studies (775 total participants) were synthesised, reporting on a wide range of biomechanical outcomes. Females were under-represented and patients in the AT group were three years older on average. Biomechanical alterations were identified in some studies during running, hopping, jumping, strength tasks and reflex activity. Equally, several biomechanical variables studied were not associated with AT in included studies, indicating a conflicting picture. Kinematics in AT patients appeared to be altered in the lower limb, potentially indicating a pattern of “medial collapse”. Muscular activity of the calf and hips was different between groups, whereby AT patients exhibited greater calf electromyographic amplitudes despite lower plantar flexor strength. Overall, dynamic maximal strength of the plantar flexors, and isometric strength of the hips might be reduced in the AT group. This systematic review reports on several biomechanical alterations in athletes with AT. With further research, these factors could potentially form treatment targets for clinicians, although clinical approaches should take other contributing health factors into account. The studies included were of low quality, and currently no solid conclusions can be drawn.
Research within the framework of Basic Psychological Need Theory (BPNT) finds strong associations between basic need frustration and depressive symptoms. This study examined the role of rumination as an underlying mechanism in the association between basic psychological need frustration and depressive symptoms. A cross-sectional sample of N = 221 adults (55.2% female, mean age = 27.95, range = 18–62, SD = 10.51) completed measures assessing their level of basic psychological need frustration, rumination, and depressive symptoms. Correlational analyses and multiple mediation models were conducted. Brooding partially mediated the relation between need frustration and depressive symptoms. BPNT and Response Styles Theory are compatible and can further advance knowledge about depression vulnerabilities.
River-valley morphology preserves information on tectonic and climatic conditions that shape landscapes. Observations suggest that river discharge and valley-wall lithology are the main controls on valley width. Yet, current models based on these observations fail to explain the full range of cross-sectional valley shapes in nature, suggesting hitherto unquantified controls on valley width. In particular, current models cannot explain the existence of paired terrace sequences that form under cyclic climate forcing. Paired river terraces are staircases of abandoned floodplains on both valley sides, and hence preserve past valley widths. Their formation requires alternating phases of predominantly river incision and predominantly lateral planation, plus progressive valley narrowing. While cyclic Quaternary climate changes can explain shifts between incision and lateral erosion, the driving mechanism of valley narrowing is unknown. Here, we extract valley geometries from climatically formed, alluvial river-terrace sequences and show that across our dataset, the total cumulative terrace height (here: total valley height) explains 90%–99% of the variance in valley width at the terrace sites. This finding suggests that valley height, or a parameter that scales linearly with valley height, controls valley width in addition to river discharge and lithology. To explain this valley-width-height relationship, we reformulate existing valley-width models and suggest that, when adjusting to new boundary conditions, alluvial valleys evolve to a width at which sediment removal from valley walls matches lateral sediment supply from hillslope erosion. Such a hillslope-channel coupling is not captured in current valley-evolution models. Our model can explain the existence of paired terrace sequences under cyclic climate forcing and relates valley width to measurable field parameters. Therefore, it facilitates the reconstruction of past climatic and tectonic conditions from valley topography.
In numerical processing, the functional role of Spatial-Numerical Associations (SNAs, such as the association of smaller numbers with left space and larger numbers with right space, the Mental Number Line hypothesis) is debated. Most studies demonstrate SNAs with lateralized responses, and there is little evidence that SNAs appear when no response is required. We recorded passive holding grip forces in no-go trials during number processing. In Experiment 1, participants performed a surface numerical decision task (“Is it a number or a letter?”). In Experiment 2, we used a deeper semantic task (“Is this number larger or smaller than five?”). Despite instruction to keep their grip force constant, participants' spontaneous grip force changed in both experiments: Smaller numbers led to larger force increase in the left than in the right hand in the numerical decision task (500–700 ms after stimulus onset). In the semantic task, smaller numbers again led to larger force increase in the left hand, and larger numbers increased the right-hand holding force. This effect appeared earlier (180 ms) and lasted longer (until 580 ms after stimulus onset). This is the first demonstration of SNAs with passive holding force. Our result suggests that (1) explicit motor response is not a prerequisite for SNAs to appear, and (2) the timing and strength of SNAs are task-dependent. (216 words).
Numerical magnitude information is assumed to be spatially represented in the form of a mental number line defined with respect to a body-centred, egocentric frame of reference. In this context, spatial language skills such as mastery of verbal descriptions of spatial position (e.g., in front of, behind, to the right/left) have been proposed to be relevant for grasping spatial relations between numerical magnitudes on the mental number line. We examined 4- to 5-year-old’s spatial language skills in tasks that allow responses in egocentric and allocentric frames of reference, as well as their relative understanding of numerical magnitude (assessed by a number word comparison task). In addition, we evaluated influences of children’s absolute understanding of numerical magnitude assessed by their number word comprehension (montring different numbers using their fingers) and of their knowledge on numerical sequences (determining predecessors and successors as well as identifying missing dice patterns of a series). Results indicated that when considering responses that corresponded to the egocentric perspective, children’s spatial language was associated significantly with their relative numerical magnitude understanding, even after controlling for covariates, such as children’s SES, mental rotation skills, and also absolute magnitude understanding or knowledge on numerical sequences. This suggests that the use of egocentric reference frames in spatial language may facilitate spatial representation of numbers along a mental number line and thus seem important for preschoolers’ relative understanding of numerical magnitude.
Wild bee species are important pollinators in agricultural landscapes. However, population decline was reported over the last decades and is still ongoing. While agricultural intensification is a major driver of the rapid loss of pollinating species, transition zones between arable fields and forest or grassland patches, i.e., agricultural buffer zones, are frequently mentioned as suitable mitigation measures to support wild bee populations and other pollinator species. Despite the reported general positive effect, it remains unclear which amount of buffer zones is needed to ensure a sustainable and permanent impact for enhancing bee diversity and abundance. To address this question at a pollinator community level, we implemented a process-based, spatially explicit simulation model of functional bee diversity dynamics in an agricultural landscape. More specifically, we introduced a variable amount of agricultural buffer zones (ABZs) at the transition of arable to grassland, or arable to forest patches to analyze the impact on bee functional diversity and functional richness. We focused our study on solitary bees in a typical agricultural area in the Northeast of Germany. Our results showed positive effects with at least 25% of virtually implemented agricultural buffer zones. However, higher amounts of ABZs of at least 75% should be considered to ensure a sufficient increase in Shannon diversity and decrease in quasi-extinction risks. These high amounts of ABZs represent effective conservation measures to safeguard the stability of pollination services provided by solitary bee species. As the model structure can be easily adapted to other mobile species in agricultural landscapes, our community approach offers the chance to compare the effectiveness of conservation measures also for other pollinator communities in future.
Dementia as one of the most prevalent diseases urges for a better understanding of the central mechanisms responsible for clinical symptoms, and necessitates improvement of actual diagnostic capabilities. The brainstem nucleus locus coeruleus (LC) is a promising target for early diagnosis because of its early structural alterations and its relationship to the functional disturbances in the patients. In this study, we applied our improved method of localisation-based LC resting-state fMRI to investigate the differences in central sensory signal processing when comparing functional connectivity (fc) of a patient group with mild cognitive impairment (MCI, n = 28) and an age-matched healthy control group (n = 29). MCI and control participants could be differentiated in their Mini-Mental-State-Examination (MMSE) scores (p < .001) and LC intensity ratio (p = .010). In the fMRI, LC fc to anterior cingulate cortex (FDR p < .001) and left anterior insula (FDR p = .012) was elevated, and LC fc to right temporoparietal junction (rTPJ, FDR p = .012) and posterior cingulate cortex (PCC, FDR p = .021) was decreased in the patient group. Importantly, LC to rTPJ connectivity was also positively correlated to MMSE scores in MCI patients (p = .017). Furthermore, we found a hyperactivation of the left-insula salience network in the MCI patients. Our results and our proposed disease model shed new light on the functional pathogenesis of MCI by directing to attentional network disturbances, which could aid new therapeutic strategies and provide a marker for diagnosis and prediction of disease progression.
The intake of high-fat diets (HFDs) containing large amounts of saturated long-chain fatty acids leads to obesity, oxidative stress, inflammation, and insulin resistance. The trace element selenium, as a crucial part of antioxidative selenoproteins, can protect against the development of diet-induced insulin resistance in white adipose tissue (WAT) by increasing glutathione peroxidase 3 (GPx3) and insulin receptor (IR) expression. Whether selenite (Se) can attenuate insulin resistance in established lipotoxic and obese conditions is unclear. We confirm that GPX3 mRNA expression in adipose tissue correlates with BMI in humans. Cultivating 3T3-L1 pre-adipocytes in palmitate-containing medium followed by Se treatment attenuates insulin resistance with enhanced GPx3 and IR expression and adipocyte differentiation. However, feeding obese mice a selenium-enriched high-fat diet (SRHFD) only resulted in a modest increase in overall selenoprotein gene expression in WAT in mice with unaltered body weight development, glucose tolerance, and insulin resistance. While Se supplementation improved adipocyte morphology, it did not alter WAT insulin sensitivity. However, mice fed a SRHFD exhibited increased insulin content in the pancreas. Overall, while selenite protects against palmitate-induced insulin resistance in vitro, obesity impedes the effect of selenite on insulin action and adipose tissue metabolism in vivo.
Cutting-edge hyperscanning methods led to a paradigm shift in social neuroscience. It allowed researchers to measure dynamic mutual alignment of neural processes between two or more individuals in naturalistic contexts. The ever-growing interest in hyperscanning research calls for the development of transparent and validated data analysis methods to further advance the field. We have developed and tested a dual electroencephalography (EEG) analysis pipeline, namely DEEP. Following the preprocessing of the data, DEEP allows users to calculate Phase Locking Values (PLVs) and cross-frequency PLVs as indices of inter-brain phase alignment of dyads as well as time-frequency responses and EEG power for each participant. The pipeline also includes scripts to control for spurious correlations. Our goal is to contribute to open and reproducible science practices by making DEEP publicly available together with an example mother-infant EEG hyperscanning dataset.
The role of the GMP nucleotides of the bis-molybdopterin guanine dinucleotide (bis-MGD) cofactor of the DMSO reductase family has long been a subject of discussion. The recent characterization of the bis-molybdopterin (bis-Mo-MPT) cofactor present in the E. coli YdhV protein, which differs from bis-MGD solely by the absence of the nucleotides, now enables studying the role of the nucleotides of bis-MGD and bis-MPT cofactors in Moco insertion and the activity of molybdoenzymes in direct comparison. Using the well-known E. coli TMAO reductase TorA as a model enzyme for cofactor insertion, we were able to show that the GMP nucleotides of bis-MGD are crucial for the insertion of the bis-MGD cofactor into apo-TorA.
Extreme habitats often harbor specific communities that differ substantially from non-extreme habitats. In many cases, these communities are characterized by archaea, bacteria and protists, whereas the number of species of metazoa and higher plants is relatively low. In extremely acidic habitats, mostly prokaryotes and protists thrive, and only very few metazoa thrive, for example, rotifers. Since many studies have investigated the physiology and ecology of individual species, there is still a gap in research on direct, trophic interactions among extremophiles. To fill this gap, we experimentally studied the trophic interactions between a predatory protist (Actinophrys sol, Heliozoa) and its prey, the rotifers Elosa woralli and Cephalodella sp., the ciliate Urosomoida sp. and the mixotrophic protist Chlamydomonas acidophila (a green phytoflagellate, Chlorophyta). We found substantial predation pressure on all animal prey. High densities of Chlamydomonas acidophila reduced the predation impact on the rotifers by interfering with the feeding behaviour of A. sol. These trophic relations represent a natural case of intraguild predation, with Chlamydomonas acidophila being the common prey and the rotifers/ciliate and A. sol being the intraguild prey and predator, respectively. We further studied this intraguild predation along a resource gradient using Cephalodella sp. as the intraguild prey. The interactions among the three species led to an increase in relative rotifer abundance with increasing resource (Chlamydomonas) densities. By applying a series of laboratory experiments, we revealed the complexity of trophic interactions within a natural extremophilic community.
Transitional Justice
(2022)
This publication deals with the topic of transitional justice. In six case studies, the authors link theoretical and practical implications in order to develop some innovative approaches. Their proposals might help to deal more effectively with the transition of societies, legal orders and political systems.
Young academics from various backgrounds provide fresh insights and demonstrate the relevance of the topic. The chapters analyse transitions and conflicts in Sierra Leone, Argentina, Nicaragua, Nepal, and South Sudan as well as Germany’s colonial genocide in Namibia. Thus, the book provides the reader with new insights and contributes to the ongoing debate about transitional justice.
Large-scale databases that report the inhibitory capacities of many combinations of candidate drug compounds and cultivated cancer cell lines have driven the development of preclinical drug-sensitivity models based on machine learning. However, cultivated cell lines have devolved from human cancer cells over years or even decades under selective pressure in culture conditions. Moreover, models that have been trained on in vitro data cannot account for interactions with other types of cells. Drug-response data that are based on patient-derived cell cultures, xenografts, and organoids, on the other hand, are not available in the quantities that are needed to train high-capacity machine-learning models. We found that pre-training deep neural network models of drug sensitivity on in vitro drug-sensitivity databases before fine-tuning the model parameters on patient-derived data improves the models’ accuracy and improves the biological plausibility of the features, compared to training only on patient-derived data. From our experiments, we can conclude that pre-trained models outperform models that have been trained on the target domains in the vast majority of cases.
The Role of the Precuneus in Human Spatial Updating in a Real Environment Setting—A cTBS Study
(2022)
As we move through an environment, we update positions of our body relative to other objects, even when some objects temporarily or permanently leave our field of view—this ability is termed egocentric spatial updating and plays an important role in everyday life. Still, our knowledge about its representation in the brain is still scarce, with previous studies using virtual movements in virtual environments or patients with brain lesions suggesting that the precuneus might play an important role. However, whether this assumption is also true when healthy humans move in real environments where full body-based cues are available in addition to the visual cues typically used in many VR studies is unclear. Therefore, in this study we investigated the role of the precuneus in egocentric spatial updating in a real environment setting in 20 healthy young participants who underwent two conditions in a cross-over design: (a) stimulation, achieved through applying continuous theta-burst stimulation (cTBS) to inhibit the precuneus and (b) sham condition (activated coil turned upside down). In both conditions, participants had to walk back with blindfolded eyes to objects they had previously memorized while walking with open eyes. Simplified trials (without spatial updating) were used as control condition, to make sure the participants were not affected by factors such as walking blindfolded, vestibular or working memory deficits. A significant interaction was found, with participants performing better in the sham condition compared to real stimulation, showing smaller errors both in distance and angle. The results of our study reveal evidence of an important role of the precuneus in a real-environment egocentric spatial updating; studies on larger samples are necessary to confirm and further investigate this finding.
We present the first systematic literature review on stress and burnout in K−12 teachers during the COVID-19 pandemic. Based on a systematic literature search, we identified 17 studies that included 9,874 K−12 teachers from around the world. These studies showed some indication that burnout did increase during the COVID-19 pandemic. There were, however, almost no differences in the levels of stress and burnout experienced by K−12 teachers compared to individuals employed in other occupational fields. School principals' leadership styles emerged as an organizational characteristic that is highly relevant for K−12 teachers' levels of stress and burnout. Individual teacher characteristics associated with burnout were K−12 teachers' personality, self-efficacy in online teaching, and perceived vulnerability to COVID-19. In order to reduce stress, there was an indication that stress-management training in combination with training in technology use for teaching may be superior to stress-management training alone. Future research needs to adopt more longitudinal designs and examine the interplay between individual and organizational characteristics in the development of teacher stress and burnout during the COVID-19 pandemic and beyond.
Background: As the number of cardiac diseases continuously increases within the last years in modern society, so does cardiac treatment, especially cardiac catheterization. The procedure of a cardiac catheterization is challenging for both patients and practitioners. Several potential stressors of psychological or physical nature can occur during the procedure. The objective of the study is to develop and implement a stress management intervention for both practitioners and patients that aims to reduce the psychological and physical strain of a cardiac catheterization.
Methods: The clinical study (DRKS00026624) includes two randomized controlled intervention trials with parallel groups, for patients with elective cardiac catheterization and practitioners at the catheterization lab, in two clinic sites of the Ernst-von-Bergmann clinic network in Brandenburg, Germany. Both groups received different interventions for stress management. The intervention for patients comprises a psychoeducational video with different stress management technics and additional a standardized medical information about the cardiac catheterization examination. The control condition includes the in hospitals practiced medical patient education before the examination (usual care). Primary and secondary outcomes are measured by physiological parameters and validated questionnaires, the day before (M1) and after (M2) the cardiac catheterization and at a postal follow-up 6 months later (M3). It is expected that people with standardized information and psychoeducation show reduced complications during cardiac catheterization procedures, better pre- and post-operative wellbeing, regeneration, mood and lower stress levels over time. The intervention for practitioners includes a Mindfulness-based stress reduction program (MBSR) over 8 weeks supervised by an experienced MBSR practitioner directly at the clinic site and an operative guideline. It is expected that practitioners with intervention show improved perceived and chronic stress, occupational health, physical and mental function, higher effort-reward balance, regeneration and quality of life. Primary and secondary outcomes are measured by physiological parameters (heart rate variability, saliva cortisol) and validated questionnaires and will be assessed before (M1) and after (M2) the MBSR intervention and at a postal follow-up 6 months later (M3). Physiological biomarkers in practitioners will be assessed before (M1) and after intervention (M2) on two work days and a two days off. Intervention effects in both groups (practitioners and patients) will be evaluated separately using multivariate variance analysis.
Discussion: This study evaluates the effectiveness of two stress management intervention programs for patients and practitioners within cardiac catheter laboratory. Study will disclose strains during a cardiac catheterization affecting both patients and practitioners. For practitioners it may contribute to improved working conditions and occupational safety, preservation of earning capacity, avoidance of participation restrictions and loss of performance. In both groups less anxiety, stress and complications before and during the procedures can be expected. The study may add knowledge how to eliminate stressful exposures and to contribute to more (psychological) security, less output losses and exhaustion during work. The evolved stress management guidelines, training manuals and the standardized patient education should be transferred into clinical routines
Objective
To improve consumer decision making, the results of risk assessments on food, feed, consumer products or chemicals need to be communicated not only to experts but also to non-expert audiences. The present study draws on evidence from literature reviews and focus groups with diverse stakeholders to identify content to integrate into an existing risk assessment communication (Risk Profile).
Methods
A combination of rapid literature reviews and focus groups with experts (risk assessors (n = 15), risk managers (n = 8)), and non-experts (general public (n = 18)) were used to identify content and strategies for including information about risk assessment results in the “Risk Profile” from the German Federal Institute for Risk Assessment. Feedback from initial focus groups was used to develop communication prototypes that informed subsequent feedback rounds in an iterative process. A final prototype was validated in usability tests with experts.
Results
Focus group feedback and suggestions from risk assessors were largely in line with findings from the literature. Risk managers and lay persons offered similar suggestions on how to improve the existing communication of risk assessment results (e.g., including more explanatory detail, reporting probabilities for individual health impairments, and specifying risks for subgroups in additional sections). Risk managers found information about quality of evidence important to communicate, whereas people from the general public found this information less relevant. Participants from lower educational backgrounds had difficulties understanding the purpose of risk assessments. User tests found that the final prototype was appropriate and feasible to implement by risk assessors.
Conclusion
An iterative and evidence-based process was used to develop content to improve the communication of risk assessments to the general public while being feasible to use by risk assessors. Remaining challenges include how to communicate dose-response relationships and standardise quality of evidence ratings across disciplines.
This study examined the spoken narrative skills of a group of bilingual Mandarin–English speaking 3–6-year-olds (N = 25) in Australia, using a remote online story-retell task. Bilingual preschoolers are an understudied population, especially those who are speaking typologically distinct languages such as Mandarin and English which have fewer structural overlaps compared to language pairs that are typologically closer, reducing cross-linguistic positive transfer. We examined these preschoolers’ spoken narrative skills as measured by macrostructures (the global organization of a story) and microstructures (linguistic structures, e.g., total number of utterances, nouns, verbs, phrases, and modifiers) across and within each language, and how various factors such as age and language experiences contribute to individual variability. The results indicate that our bilingual preschoolers acquired spoken narrative skills similarly across their two languages, i.e., showing similar patterns of productivity for macrostructure and microstructure elements in both of their two languages. While chronological age was positively correlated with macrostructures in both languages (showing developmental effects), there were no significant correlations between measures of language experiences and the measures of spoken narrative skills (no effects for language input/output). The findings suggest that although these preschoolers acquire two typologically diverse languages in different learning environments, Mandarin at home with highly educated parents, and English at preschool, they displayed similar levels of oral narrative skills as far as these macro−/micro-structure measures are concerned. This study provides further evidence for the feasibility of remote online assessment of preschoolers’ narrative skills.
We collect a network dataset of tenured economics faculty in Austria, Germany and Switzerland. We rank the 100 institutions included with a minimum violation ranking. This ranking is positively and significantly correlated with the Times Higher Education ranking of economics institutions. According to the network ranking, individuals on average go down about 23 ranks from their doctoral institution to their employing institution. While the share of females in our dataset is only 15%, we do not observe a significant gender hiring gap (a difference in rank changes between male and female faculty). We conduct a robustness check with the Handelsblatt and the Times Higher Education ranking. According to these rankings, individuals on average go down only about two ranks. We do not observe a significant gender hiring gap using these two rankings (although the dataset underlying this analysis is small and these estimates are likely to be noisy). Finally, we discuss the limitations of the network ranking in our context.
Older adults with amnestic mild cognitive impairment (aMCI) who in addition to their memory deficits also suffer from frontal-executive dysfunctions have a higher risk of developing dementia later in their lives than older adults with aMCI without executive deficits and older adults with non-amnestic MCI (naMCI). Handgrip strength (HGS) is also correlated with the risk of cognitive decline in the elderly. Hence, the current study aimed to investigate the associations between HGS and executive functioning in individuals with aMCI, naMCI and healthy controls. Older, right-handed adults with amnestic MCI (aMCI), non-amnestic MCI (naMCI), and healthy controls (HC) conducted a handgrip strength measurement via a handheld dynamometer. Executive functions were assessed with the Trail Making Test (TMT A&B). Normalized handgrip strength (nHGS, normalized to Body Mass Index (BMI)) was calculated and its associations with executive functions (operationalized through z-scores of TMT B/A ratio) were investigated through partial correlation analyses (i.e., accounting for age, sex, and severity of depressive symptoms). A positive and low-to-moderate correlation between right nHGS (rp (22) = 0.364; p = 0.063) and left nHGS (rp (22) = 0.420; p = 0.037) and executive functioning in older adults with aMCI but not in naMCI or HC was observed. Our results suggest that higher levels of nHGS are linked to better executive functioning in aMCI but not naMCI and HC. This relationship is perhaps driven by alterations in the integrity of the hippocampal-prefrontal network occurring in older adults with aMCI. Further research is needed to provide empirical evidence for this assumption.
There is a large variety of goals instructors have for laboratory courses, with different courses focusing on different subsets of goals. An often implicit, but crucial, goal is to develop students’ attitudes, views, and expectations about experimental physics to align with practicing experimental physicists. The assessment of laboratory courses upon this one dimension of learning has been intensively studied in U.S. institutions using the Colorado Learning Attitudes about Science Survey for Experimental Physics (E-CLASS). However, there is no such an instrument available to use in Germany, and the influence of laboratory courses on students views about the nature of experimental physics is still unexplored at German-speaking institutions. Motivated by the lack of an assessment tool to investigate this goal in laboratory courses at German-speaking institutions, we present a translated version of the E-CLASS adapted to the context at German-speaking institutions. We call the German version of the E-CLASS, the GE-CLASS. We describe the translation process and the creation of an automated web-based system for instructors to assess their laboratory courses. We also present first results using GE-CLASS obtained at the University of Potsdam. A first comparison between E-CLASS and GE-CLASS results shows clear differences between University of Potsdam and U.S. students’ views and beliefs about experimental physics.
Intelligence, as well as working memory and attention, affect the acquisition of mathematical competencies. This paper aimed to examine the influence of working memory and attention when taking different mathematical skills into account as a function of children’s intellectual ability. Overall, intelligence, working memory, attention and numerical skills were assessed twice in 1868 German pre-school children (t1, t2) and again at 2nd grade (t3). We defined three intellectual ability groups based on the results of intellectual assessment at t1 and t2. Group comparisons revealed significant differences between the three intellectual ability groups. Over time, children with low intellectual ability showed the lowest achievement in domain-general and numerical and mathematical skills compared to children of average intellectual ability. The highest achievement on the aforementioned variables was found for children of high intellectual ability. Additionally, path modelling revealed that, depending on the intellectual ability, different models of varying complexity could be generated. These models differed with regard to the relevance of the predictors (t2) and the future mathematical skills (t3). Causes and conclusions of these findings are discussed.
Isoflux tension propagation (IFTP) theory and Langevin dynamics (LD) simulations are employed to study the dynamics of channel-driven polymer translocation in which a polymer translocates into a narrow channel and the monomers in the channel experience a driving force fc. In the high driving force limit, regardless of the channel width, IFTP theory predicts τ ∝ f βc for the translocation time, where β = −1 is the force scaling exponent. Moreover, LD data show that for a very narrow channel fitting only a single file of monomers, the entropic force due to the subchain inside the channel does not play a significant role in the translocation dynamics and the force exponent β = −1 regardless of the force magnitude. As the channel width increases the number of possible spatial configurations of the subchain inside the channel becomes significant and the resulting entropic force causes the force exponent to drop below unity.
Anomalous-diffusion, the departure of the spreading dynamics of diffusing particles from the traditional law of Brownian-motion, is a signature feature of a large number of complex soft-matter and biological systems. Anomalous-diffusion emerges due to a variety of physical mechanisms, e.g., trapping interactions or the viscoelasticity of the environment. However, sometimes systems dynamics are erroneously claimed to be anomalous, despite the fact that the true motion is Brownian—or vice versa. This ambiguity in establishing whether the dynamics as normal or anomalous can have far-reaching consequences, e.g., in predictions for reaction- or relaxation-laws. Demonstrating that a system exhibits normal- or anomalous-diffusion is highly desirable for a vast host of applications. Here, we present a criterion for anomalous-diffusion based on the method of power-spectral analysis of single trajectories. The robustness of this criterion is studied for trajectories of fractional-Brownian-motion, a ubiquitous stochastic process for the description of anomalous-diffusion, in the presence of two types of measurement errors. In particular, we find that our criterion is very robust for subdiffusion. Various tests on surrogate data in absence or presence of additional positional noise demonstrate the efficacy of this method in practical contexts. Finally, we provide a proof-of-concept based on diverse experiments exhibiting both normal and anomalous-diffusion.
Symmetric, elegantly entangled structures are a curious mathematical construction that has found their way into the heart of the chemistry lab and the toolbox of constructive geometry. Of particular interest are those structures—knots, links and weavings—which are composed locally of simple twisted strands and are globally symmetric. This paper considers the symmetric tangling of multiple 2-periodic honeycomb networks. We do this using a constructive methodology borrowing elements of graph theory, low-dimensional topology and geometry. The result is a wide-ranging enumeration of symmetric tangled honeycomb networks, providing a foundation for their exploration in both the chemistry lab and the geometers toolbox.
Studies have revealed mixed results on how antidepressant drugs affect lipid profiles of patients with major depression disorder (MDD). Even less is known about how patients respond to a switch of antidepressant medication with respect to their metabolic profile. For this, effects of a switch in antidepressants medication on lipid markers were studied in MDD patients. 15 participants (females = 86.67%; males = 13.33%; age: 49.45 ± 7.45 years) with MDD and a prescribed switch in their antidepressant medication were recruited at a psychosomatic rehabilitation clinic. Participants were characterized (with questionnaires and blood samples) at admission to the rehabilitation clinic (baseline, T0) and followed up with a blood sample two weeks (T1) later. HDL, LDL, total cholesterol, and triglycerides were determined (T0), and their change analyzed (Wilcoxon test) at follow up (T1). Decrements in HDL (p = 0.041), LDL (p < 0.001), and total cholesterol (p < 0.001) were observed two weeks after a switch in antidepressant medication. Triglycerides showed no difference (p = 0.699). Overall, LDL, HDL, and total cholesterol are affected by a change in antidepressant drugs in patients with MDD. These observations are of clinical relevance for medical practitioners in the planning and management of treatment strategies for MDD patients.
Cardiovascular diseases are the main cause of death worldwide, and their prevalence is expected to rise in the coming years. Polymer-based artificial replacements have been widely used for the treatment of cardiovascular diseases. Coagulation and thrombus formation on the interfaces between the materials and the human physiological environment are key issues leading to the failure of the medical device in clinical implantation. The surface properties of the materials have a strong influence on the protein adsorption and can direct the blood cell adhesion behavior on the interfaces. Furthermore, implant-associated infections will be induced by bacterial adhesion and subsequent biofilm formation at the implantation site. Thus, it is important to improve the hemocompatibility of an implant by altering the surface properties. One of the effective strategies is surface passivation to achieve protein/cell repelling ability to reduce the risk of thrombosis.
This thesis consists of synthesis, functionalization, sterilization, and biological evaluation of bulk poly(glycerol glycidyl ether) (polyGGE), which is a highly crosslinked polyether-based polymer synthesized by cationic ring-opening polymerization. PolyGGE is hypothesized to be able to resist plasma protein adsorption and bacterial adhesion due to analogous chemical structure as polyethylene glycol and hyperbranched polyglycerol. Hydroxyl end groups of polyGGE provide possibilities to be functionalized with sulfates to mimic the anti-thrombogenic function of the endothelial glycocalyx.
PolyGGE was synthesized by polymerization of the commercially available monomer glycerol glycidyl ether, which was characterized as a mixture of mono-, di- and tri-glycidyl ether. Cationic ring opening-polymerization of this monomer was carried out by ultraviolet (UV) initiation of the photo-initiator diphenyliodonium hexafluorophosphate. With the increased UV curing time, more epoxides in the side chains of the monomers participated in chemical crosslinking, resulting in an increase of Young’s modulus, while the value of elongation at break of polyGGE first increased due to the propagation of the polymer chains then decreased with the increase of crosslinking density. Eventually, the chain propagation can be effectively terminated by potassium hydroxide aqueous solution. PolyGGE exhibited different tensile properties in hydrated conditions at body temperature compared to the values in the dry state at room temperature. Both Young’s modulus and values of elongation at break were remarkably reduced when tested in water at 37 °C, which was above the glass transition temperature of polyGGE. At physiological conditions, entanglements of the ployGGE networks unfolded and the free volume of networks were replaced by water molecules as softener, which increased the mobility of the polymer chains, resulting in a lower Young’s modulus.
Protein adsorption analysis was performed on polyGGE films with 30 min UV curing using an enzyme-linked immunosorbent assay. PolyGGE could effectively prevent the adsorption of human plasma fibrinogen, albumin, and fibronectin at the interface of human plasma and polyGGE films. The protein resistance of polyGGE was comparable to the negative controls: the hemocompatible polydimethylsiloxane (PDMS), showing its potential as a coating material for cardiovascular implants. Moreover, antimicrobial tests of bacterial activity using isothermal microcalorimetry and the microscopic image of direct bacteria culturing demonstrated that polyGGE could directly interfere biofilm formation and growth of both Gram-negative and antibiotic-resistant Gram-positive bacteria, indicating the potential application of polyGGE for combating the risk of hospital-acquired infections and preventing drug-resistant superbug spreading.
To investigate its cell compatibility, polyGGE films were extracted by different solvents (ethanol, chloroform, acetone) and cell culture medium. Indirect cytotoxicity tests showed extracted polyGGE films still had toxic effects on L929 fibroblast cells. High-performance liquid chromatography/electrospray ionization mass spectrometry revealed the occurrence of organochlorine-containing compounds released during the polymer-cell culture medium interaction. A constant level of those organochlorine-containing compounds was confirmed from GGE monomer by a specific peak of C-Cl stretching in infrared spectra of GGE. This is assumed to be the main reason causing the increased cell membrane permeability and decreased metabolic activity, leading to cell death. Attempts as changing solvents were made to remove toxic substances, however, the release of these small molecules seems to be sluggish. The densely crosslinked polyGGE networks can possibly contribute to the trapping of organochlorine-containing compounds. These results provide valuable information for exploring the potentially toxic substances, leaching from polyGGE networks, and propose a feasible strategy for minimizing the cytotoxicity via reducing their crosslinking density.
Sulfamic acid/ N-Methyl-2-pyrrolidone (NMP) were selected as the reagents for the sulfation of polyGGE surfaces. Fourier transform attenuated total reflection infrared spectroscopy (ATR-FT-IR) was used to monitor the functionalization kinetics and the results confirmed the successful sulfate grafting on the surface of polyGGE with the covalent bond -C-O-S-. X-ray photoelectron spectroscopy was used to determine the element composition on the surface and the cross-section of the functionalized polyGGE and sulfation within 15 min guarantees the sulfation only takes place on the surface while not occurring in the bulk of the polymer. The concentration of grafted sulfates increased with the increasing reaction time. The hydrophilicity of the surface of polyGGE was highly increased due to the increase of negatively charged end groups. Three sterilization techniques including autoclaving, gamma irradiation, and ethylene oxide (EtO) sterilization were used for polyGGE sulfates. Results from ATR-FT-IR and Toluidine Blue O quantitative assay demonstrated the total loss of the sulfates after autoclave sterilization, which was also confirmed by the increased water contact angle. Little influence on the concentration of sulfates was found for gamma-irradiated and autoclaving sterilized polyGGE sulfates. To investigate the thermal influence on polyGGE sulfates, one strategy was to use poly(hydroxyethyl acrylate) sulfates (PHEAS) for modeling. The thermogravimetric analysis profile of PHEAS demonstrated that sulfates are not thermally stable independent of the substrate materials and decomposition of sulfates occurs at around 100 °C. Although gamma irradiation also showed little negative effect on the sulfate content, the color change in the polyGGE sulfates indicates chemical or physical change might occur in the polymer. EtO sterilization was validated as the most suitable sterilization technique to maintain the chemical structure of polyGGE sulfates.
In conclusion, the conducted work proved that bulk polyGGE can be used as an antifouling coating material and shows its antimicrobial potential. Sulfates functionalization can be effectively realized using sulfamic acid/NMP. EtO sterilization is the most suitable sterilization technique for grafted sulfates. Besides, this thesis also offers a good strategy for the analysis of toxic leachable substances using suitable physicochemical characterization techniques. Future work will focus on minimizing/eliminating the release of toxic substances via reducing the crosslinking density. Another interesting aspect is to study whether grafted sulfates can meet the need for anti-thrombogenicity.
Plate tectonics describes the movement of rigid plates at the surface of the Earth as well as their complex deformation at three types of plate boundaries: 1) divergent boundaries such as rift zones and mid-ocean ridges, 2) strike-slip boundaries where plates grind past each other, such as the San Andreas Fault, and 3) convergent boundaries that form large mountain ranges like the Andes. The generally narrow deformation zones that bound the plates exhibit complex strain patterns that evolve through time. During this evolution, plate boundary deformation is driven by tectonic forces arising from Earth’s deep interior and from within the lithosphere, but also by surface processes, which erode topographic highs and deposit the resulting sediment into regions of low elevation. Through the combination of these factors, the surface of the Earth evolves in a highly dynamic way with several feedback mechanisms. At divergent boundaries, for example, tensional stresses thin the lithosphere, forcing uplift and subsequent erosion of rift flanks, which creates a sediment source. Meanwhile, the rift center subsides and becomes a topographic low where sediments accumulate. This mass transfer from foot- to hanging wall plays an important role during rifting, as it prolongs the activity of individual normal faults. When rifting continues, continents are eventually split apart, exhuming Earth’s mantle and creating new oceanic crust. Because of the complex interplay between deep tectonic forces that shape plate boundaries and mass redistribution at the Earth’s surface, it is vital to understand feedbacks between the two domains and how they shape our planet.
In this study I aim to provide insight on two primary questions: 1) How do divergent and strike-slip plate boundaries evolve? 2) How is this evolution, on a large temporal scale and a smaller structural scale, affected by the alteration of the surface through erosion and deposition? This is done in three chapters that examine the evolution of divergent and strike-slip plate boundaries using numerical models. Chapter 2 takes a detailed look at the evolution of rift systems using two-dimensional models. Specifically, I extract faults from a range of rift models and correlate them through time to examine how fault networks evolve in space and time. By implementing a two-way coupling between the geodynamic code ASPECT and landscape evolution code FastScape, I investigate how the fault network and rift evolution are influenced by the system’s erosional efficiency, which represents many factors like lithology or climate. In Chapter 3, I examine rift evolution from a three-dimensional perspective. In this chapter I study linkage modes for offset rifts to determine when fast-rotating plate-boundary structures known as continental microplates form. Chapter 4 uses the two-way numerical coupling between tectonics and landscape evolution to investigate how a strike-slip boundary responds to large sediment loads, and whether this is sufficient to form an entirely new type of flexural strike-slip basin.
One aspect of achieving a more sustainable chemical industry is the minimization of the usage of solvents and chemicals. Thus, optimization and development of chemical processes for large-scale production is favourably performed in small batches. The critical step in this approach is upscaling the batches from the small reaction systems to the large reactors mandatory for cost efficient production in an industrial environment. Scaling up the bulk volume always goes along with increasing the surface where the reaction medium is in contact with the confining vessel. Since volume scales proportional with the cubic dimension while the surface scales quadratic, their ratio is size-dependent. The influence of reaction vessel walls can change the reaction performance. A number of phenomena occurring at the surface-liquid interface can affect reaction rates and yields, resulting in possible difficulties in predicting and extrapolating from small size production scale to large industrial processes. The application of levitated droplets as a containerless reaction vessels provides a promising possibility to avoid the above-mentioned issues.
In the presented work, an efficient coupling of acoustically levitated droplets to an ion mobility (IM) spectrometer, operating at ambient conditions, was designed for real-time monitoring of chemical reactions. The design of the system comprises noncontact sampling and ionization of the droplet realised by laser desorption/ionization at 2,94 µm. The scope of the work includes fundamental studies covering understanding of laser irradiation of droplets enclosed in an acoustical field. Understanding of this phenomenon is crucial to comprehending the effects of temporal and spatial resolution of the generated ion plume that influence the resolution of the system.
The set-up includes an acoustic trap, laser irradiation and ion manipulation electrostatic lenses operating at high voltage at ambient pressure. The complexity of the design needs to fully be considered for an effective ion transfer at the interface region between the levitated droplet and IM spectrometer. For sampling and ionization, two distinct laser pulse lengths were evaluated, ns and µs. Irradiation via µs laser pulses provides several advantages: i) the droplet volume is not extensively impinged, as in case of ns laser pulses, allowing the sampling of only the small volume of the droplet; ii) the lower fluence results in less pronounced oscillations of the droplet confined in the acoustic field. The droplet will not be dissipated out of the acoustic field leading to loss of the sample; iii) the mild laser irradiation results in better spatial and temporal ion plume confinement, leading to better resolution of the detected ion packets. Finally, this knowledge allows the application of ion optics necessary to induce ion flow between the droplet suspended in the acoustic field and the IM spectrometer. The ion optics, composed of 2 electrostatic lenses placed in the near vicinity of the droplet, allow effective focusing of the ion plume and its redirection directly to the IM spectrometer entrance. This novel coupling has proved to be successful for detection of some simple molecules ionizable at the 2.94 µm wavelength. To further demonstrate the applicability of the system, a proof-of-principle reaction was selected, fulfilling the requirements of the system, and was subjected to comprehensive investigation of its performance. Herein, the reaction between N-Boc cysteine methyl ester and allyl alcohol has been performed in a batch reactor and on-line monitored via 1H NMR to establish reaction propagation. With the additional assessment, it was confirmed that the thiol-ene coupling can be performed within first 20 minutes of the irradiation with a reaction yield above 50%, proving that the reaction can be applied as a study case to assess the possibilities of the developed system.
The echo chamber model describes the development of groups in heterogeneous social networks. By heterogeneous social network we mean a set of individuals, each of whom represents exactly one opinion. The existing relationships between individuals can then be represented by a graph. The echo chamber model is a time-discrete model which, like a board game, is played in rounds. In each round, an existing relationship is randomly and uniformly selected from the network and the two connected individuals interact. If the opinions of the individuals involved are sufficiently similar, they continue to move closer together in their opinions, whereas in the case of opinions that are too far apart, they break off their relationship and one of the individuals seeks a new relationship. In this paper we examine the building blocks of this model. We start from the observation that changes in the structure of relationships in the network can be described by a system of interacting particles in a more abstract space.
These reflections lead to the definition of a new abstract graph that encompasses all possible relational configurations of the social network. This provides us with the geometric understanding necessary to analyse the dynamic components of the echo chamber model in Part III. As a first step, in Part 7, we leave aside the opinions of the inidividuals and assume that the position of the edges changes with each move as described above, in order to obtain a basic understanding of the underlying dynamics. Using Markov chain theory, we find upper bounds on the speed of convergence of an associated Markov chain to its unique stationary distribution and show that there are mutually identifiable networks that are not apparent in the dynamics under analysis, in the sense that the stationary distribution of the associated Markov chain gives equal weight to these networks.
In the reversible cases, we focus in particular on the explicit form of the stationary distribution as well as on the lower bounds of the Cheeger constant to describe the convergence speed.
The final result of Section 8, based on absorbing Markov chains, shows that in a reduced version of the echo chamber model, a hierarchical structure of the number of conflicting relations can be identified.
We can use this structure to determine an upper bound on the expected absorption time, using a quasi-stationary distribution. This hierarchy of structure also provides a bridge to classical theories of pure death processes. We conclude by showing how future research can exploit this link and by discussing the importance of the results as building blocks for a full theoretical understanding of the echo chamber model. Finally, Part IV presents a published paper on the birth-death process with partial catastrophe. The paper is based on the explicit calculation of the first moment of a catastrophe. This first part is entirely based on an analytical approach to second degree recurrences with linear coefficients. The convergence to 0 of the resulting sequence as well as the speed of convergence are proved. On the other hand, the determination of the upper bounds of the expected value of the population size as well as its variance and the difference between the determined upper bound and the actual value of the expected value. For these results we use almost exclusively the theory of ordinary nonlinear differential equations.
Biofilms are complex living materials that form as bacteria get embedded in a matrix of self-produced protein and polysaccharide fibres. The formation of a network of extracellular biopolymer fibres contributes to the cohesion of the biofilm by promoting cell-cell attachment and by mediating biofilm-substrate interactions. This sessile mode of bacteria growth has been well studied by microbiologists to prevent the detrimental effects of biofilms in medical and industrial settings. Indeed, biofilms are associated with increased antibiotic resistance in bacterial infections, and they can also cause clogging of pipelines or promote bio-corrosion. However, biofilms also gained interest from biophysics due to their ability to form complex morphological patterns during growth. Recently, the emerging field of engineered living materials investigates biofilm mechanical properties at multiple length scales and leverages the tools of synthetic biology to tune the functions of their constitutive biopolymers.
This doctoral thesis aims at clarifying how the morphogenesis of Escherichia coli (E. coli) biofilms is influenced by their growth dynamics and mechanical properties. To address this question, I used methods from cell mechanics and materials science. I first studied how biological activity in biofilms gives rise to non-uniform growth patterns. In a second study, I investigated how E. coli biofilm morphogenesis and its mechanical properties adapt to an environmental stimulus, namely the water content of their substrate. Finally, I estimated how the mechanical properties of E. coli biofilms are altered when the bacteria express different extracellular biopolymers.
On nutritive hydrogels, micron-sized E. coli cells can build centimetre-large biofilms. During this process, bacterial proliferation and matrix production introduce mechanical stresses in the biofilm, which release through the formation of macroscopic wrinkles and delaminated buckles. To relate these biological and mechanical phenomena, I used time-lapse fluorescence imaging to track cell and matrix surface densities through the early and late stages of E. coli biofilm growth. Colocalization of high cell and matrix densities at the periphery precede the onset of mechanical instabilities at this annular region. Early growth is detected at this outer annulus, which was analysed by adding fluorescent microspheres to the bacterial inoculum. But only when high rates of matrix production are present in the biofilm centre, does overall biofilm spreading initiate along the solid-air interface. By tracking larger fluorescent particles for a long time, I could distinguish several kinematic stages of E. coli biofilm expansion and observed a transition from non-linear to linear velocity profiles, which precedes the emergence of wrinkles at the biofilm periphery. Decomposing particle velocities to their radial and circumferential components revealed a last kinematic stage, where biofilm movement is mostly directed towards the radial delaminated buckles, which verticalize. The resulting compressive strains computed in these regions were observed to substantially deform the underlying agar substrates. The co-localization of higher cell and matrix densities towards an annular region and the succession of several kinematic stages are thus expected to promote the emergence of mechanical instabilities at the biofilm periphery. These experimental findings are predicted to advance future modelling approaches of biofilm morphogenesis.
E. coli biofilm morphogenesis is further anticipated to depend on external stimuli from the environment. To clarify how the water could be used to tune biofilm material properties, we quantified E. coli biofilm growth, wrinkling dynamics and rigidity as a function of the water content of the nutritive substrates. Time-lapse microscopy and computational image analysis revealed that substrates with high water content promote biofilm spreading kinetics, while substrates with low water content promote biofilm wrinkling. The wrinkles observed on biofilm cross-sections appeared more bent on substrates with high water content, while they tended to be more vertical on substrates with low water content. Both wet and dry biomass, accumulated over 4 days of culture, were larger in biofilms cultured on substrates with high water content, despite extra porosity within the matrix layer. Finally, the micro-indentation analysis revealed that substrates with low water content supported the formation of stiffer biofilms. This study shows that E. coli biofilms respond to the water content of their substrate, which might be used for tuning their material properties in view of further applications.
Biofilm material properties further depend on the composition and structure of the matrix of extracellular proteins and polysaccharides. In particular, E. coli biofilms were suggested to present tissue-like elasticity due to a dense fibre network consisting of amyloid curli and phosphoethanolamine-modified cellulose. To understand the contribution of these components to the emergent mechanical properties of E. coli biofilms, we performed micro-indentation on biofilms grown from bacteria of several strains. Besides showing higher dry masses, larger spreading diameters and slightly reduced water contents, biofilms expressing both main matrix components also presented high rigidities in the range of several hundred kPa, similar to biofilms containing only curli fibres. In contrast, a lack of amyloid curli fibres provides much higher adhesive energies and more viscoelastic fluid-like material behaviour. Therefore, the combination of amyloid curli and phosphoethanolamine-modified cellulose fibres implies the formation of a composite material whereby the amyloid curli fibres provide rigidity to E. coli biofilms, whereas the phosphoethanolamine-modified cellulose rather acts as a glue. These findings motivate further studies involving purified versions of these protein and polysaccharide components to better understand how their interactions benefit biofilm functions.
All three studies depict different aspects of biofilm morphogenesis, which are interrelated. The first work reveals the correlation between non-uniform biological activities and the emergence of mechanical instabilities in the biofilm. The second work acknowledges the adaptive nature of E. coli biofilm morphogenesis and its mechanical properties to an environmental stimulus, namely water. Finally, the last study reveals the complementary role of the individual matrix components in the formation of a stable biofilm material, which not only forms complex morphologies but also functions as a protective shield for the bacteria it contains. Our experimental findings on E. coli biofilm morphogenesis and their mechanical properties can have further implications for fundamental and applied biofilm research fields.
Metabolic derangement with poor glycemic control accompanying overweight and obesity is associated with chronic low-grade inflammation and hyperinsulinemia. Macrophages, which present a very heterogeneous population of cells, play a key role in the maintenance of normal tissue homeostasis, but functional alterations in the resident macrophage pool as well as newly recruited monocyte-derived macrophages are important drivers in the development of low-grade inflammation. While metabolic dysfunction, insulin resistance and tissue damage may trigger or advance pro-inflammatory responses in macrophages, the inflammation itself contributes to the development of insulin resistance and the resulting hyperinsulinemia. Macrophages express insulin receptors whose downstream signaling networks share a number of knots with the signaling pathways of pattern recognition and cytokine receptors, which shape macrophage polarity. The shared knots allow insulin to enhance or attenuate both pro-inflammatory and anti-inflammatory macrophage responses. This supposedly physiological function may be impaired by hyperinsulinemia or insulin resistance in macrophages. This review discusses the mutual ambiguous relationship of low-grade inflammation, insulin resistance, hyperinsulinemia and the insulin-dependent modulation of macrophage activity with a focus on adipose tissue and liver.
Salt deposits offer a variety of usage types. These include the mining of rock salt and potash salt as important raw materials, the storage of energy in man-made underground caverns, and the disposal of hazardous substances in former mines. The most serious risk with any of these usage types comes from the contact with groundwater or surface water. It causes an uncontrolled dissolution of salt rock, which in the worst case can result in the flooding or collapse of underground facilities. Especially along potash seams, cavernous structures can spread quickly, because potash salts show a much higher solubility than rock salt. However, as their chemical behavior is quite complex, previous models do not account for these highly soluble interlayers. Therefore, the objective of the present thesis is to describe the evolution of cavernous structures along potash seams in space and time in order to improve hazard mitigation during the utilization of salt deposits.
The formation of cavernous structures represents an interplay of chemical and hydraulic processes. Hence, the first step is to systematically investigate the dissolution and precipitation reactions that occur when water and potash salt come into contact. For this purpose, a geochemical reaction model is used. The results show that the minerals are only partially dissolved, resulting in a porous sponge like structure. With the saturation of the solution increasing, various secondary minerals are formed, whose number and type depend on the original rock composition. Field data confirm a correlation between the degree of saturation and the distance from the center of the cavern, where solution is entering. Subsequently, the reaction model is coupled with a flow and transport code and supplemented by a novel approach called ‘interchange’. The latter enables the exchange of solution and rock between areas of different porosity and mineralogy, and thus ultimately the growth of the cavernous structure. By means of several scenario analyses, cavern shape, growth rate and mineralogy are systematically investigated, taking also heterogeneous potash seams into account. The results show that basically four different cases can be distinguished, with mixed forms being a frequent occurrence in nature. The classification scheme is based on the dimensionless numbers Péclet and Damköhler, and allows for a first assessment of the hazard potential. In future, the model can be applied to any field case, using measurement data for calibration.
The presented research work provides a reactive transport model that is able to spatially and temporally characterize the propagation of cavernous structures along potash seams for the first time. Furthermore, it allows to determine thickness and composition of transition zones between cavern center and unaffected salt rock. The latter is particularly important in potash mining, so that natural cavernous structures can be located at an early stage and the risk of mine flooding can thus be reduced. The models may also contribute to an improved hazard prevention in the construction of storage caverns and the disposal of hazardous waste in salt deposits. Predictions regarding the characteristics and evolution of cavernous structures enable a better assessment of potential hazards, such as integrity or stability loss, as well as of suitable mitigation measures.
Localisation of deformation is a ubiquitous feature in continental rift dynamics and observed across drastically different time and length scales. This thesis comprises one experimental and two numerical modelling studies investigating strain localisation in (1) a ductile shear zone induced by a material heterogeneity and (2) in an active continental rift setting. The studies are related by the fact that the weakening mechanisms on the crystallographic and grain size scale enable bulk rock weakening, which fundamentally enables the formation of shear zones, continental rifts and hence plate tectonics. Aiming to investigate the controlling mechanisms on initiation and evolution of a shear zone, the torsion experiments of the experimental study were conducted in a Patterson type apparatus with strong Carrara marble cylinders with a weak, planar Solnhofen limestone inclusion. Using state-of-the-art numerical modelling software, the torsion experiments were simulated to answer questions regarding localisation procedure like stress distribution or the impact of rheological weakening. 2D numerical models were also employed to integrate geophysical and geological data to explain characteristic tectonic evolution of the Southern and Central Kenya Rift. Key elements of the numerical tools are a randomized initial strain distribution and the usage of strain softening. During the torsion experiments, deformation begins to localise at the limestone inclusion tips in a process zone, which propagates into the marble matrix with increasing deformation until a ductile shear zone is established. Minor indicators for coexisting brittle deformation are found close to the inclusion tip and presumed to slightly facilitate strain localisation besides the dominant ductile deformation processes. The 2D numerical model of the torsion experiment successfully predicts local stress concentration and strain rate amplification ahead of the inclusion in first order agreement with the experimental results. A simple linear parametrization of strain weaking enables high accuracy reproduction of phenomenological aspects of the observed weakening. The torsion experiments suggest that loading conditions do not affect strain localisation during high temperature deformation of multiphase material with high viscosity contrasts. A numerical simulation can provide a way of analysing the process zone evolution virtually and extend the examinable frame. Furthermore, the nested structure and anastomosing shape of an ultramylonite band was mimicked with an additional second softening step. Rheological weakening is necessary to establish a shear zone in a strong matrix around a weak inclusion and for ultramylonite formation.
Such strain weakening laws are also incorporated into the numerical models of the
Southern and Central Kenya Rift that capture the characteristic tectonic evolution. A three-stage early rift evolution is suggested that starts with (1) the accommodation of strain by a single border fault and flexure of the hanging-wall crust, after which (2) faulting in the hanging-wall and the basin centre increases before (3) the early-stage asymmetry is lost and basinward localisation of deformation occurs. Along-strike variability of rifts can be produced by modifying the initial random noise distribution. In summary, the three studies address selected aspects of the broad range of mechanisms and processes that fundamentally enable the deformation of rock and govern the localisation patterns across the scales. In addition to the aforementioned results, the first and second manuscripts combined, demonstrate a procedure to find new or improve on existing numerical formulations for specific rheologies and their dynamic weakening. These formulations are essential in addressing rock deformation from the grain to the global scale. As within the third study of this thesis, where geodynamic controls on the evolution of a rift were examined and acquired by the integration of geological and geophysical data into a numerical model.
What are the consequences of unemployment and precarious employment for individuals' health in Europe? What are the moderating factors that may offset (or increase) the health consequences of labor-market risks? How do the effects of these risks vary across different contexts, which differ in their institutional and cultural settings? Does gender, regarded as a social structure, play a role, and how? To answer these questions is the aim of my cumulative thesis. This study aims to advance our knowledge about the health consequences that unemployment and precariousness cause over the life course. In particular, I investigate how several moderating factors, such as gender, the family, and the broader cultural and institutional context, may offset or increase the impact of employment instability and insecurity on individual health.
In my first paper, 'The buffering role of the family in the relationship between job loss and self-perceived health: Longitudinal results from Europe, 2004-2011', I and my co-authors measure the causal effect of job loss on health and the role of the family and welfare states (regimes) as moderating factors. Using EU-SILC longitudinal data (2004-2011), we estimate the probability of experiencing 'bad health' following a transition to unemployment by applying linear probability models and undertake separate analyses for men and women. Firstly, we measure whether changes in the independent variable 'job loss' lead to changes in the dependent variable 'self-rated health' for men and women separately. Then, by adding into the model different interaction terms, we measure the moderating effect of the family, both in terms of emotional and economic support, and how much it varies across different welfare regimes. As an identification strategy, we first implement static fixed-effect panel models, which control for time-varying observables and indirect health selection—i.e., constant unobserved heterogeneity. Secondly, to control for reverse causality and path dependency, we implement dynamic fixed-effect panel models, adding a lagged dependent variable to the model.
We explore the role of the family by focusing on close ties within households: we consider the presence of a stable partner and his/her working status as a source of social and economic support. According to previous literature, having a partner should reduce the stress from adverse events, thanks to the symbolic and emotional dimensions that such a relationship entails, regardless of any economic benefits. Our results, however, suggest that benefits linked to the presence of a (female) partner also come from the financial stability that (s)he can provide in terms of a second income. Furthermore, we find partners' employment to be at least as important as the mere presence of the partner in reducing the negative effect of job loss on the individual's health by maintaining the household's standard of living and decreasing economic strain on the family. Our results are in line with previous research, which has highlighted that some people cope better than others with adverse life circumstances, and the support provided by the family is a crucial resource in that regard.
We also reported an important interaction between the family and the welfare state in moderating the health consequences of unemployment, showing how the compensation effect of the family varies across welfare regimes. The family plays a decisive role in cushioning the adverse consequences of labor market risks in Southern and Eastern welfare states, characterized by less developed social protection systems and –especially the Southern – high level of familialism.
The first paper also found important gender differences concerning job loss, family and welfare effects. Of particular interest is the evidence suggesting that health selection works differently for men and women, playing a more prominent role for women than for men in explaining the relationship between job loss and self-perceived health. The second paper, 'Gender roles and selection mechanisms across contexts: A comparative analysis of the relationship between unemployment, self-perceived health, and gender.' investigates more in-depth the gender differential in health driven by unemployment.
Being a highly contested issue in literature, we aim to study whether men are more penalized than women or the other way around and the mechanisms that may explain the gender difference. To do that, we rely on two theoretical arguments: the availability of alternative roles and social selection. The first argument builds on the idea that men and women may compensate for the detrimental health consequences of unemployment through the commitment to 'alternative roles,' which can provide for the resources needed to fulfill people's socially constructed needs. Notably, the availability of alternative options depends on the different positions that men and women have in society.
Further, we merge the availability of the 'alternative roles' argument with the health selection argument. We assume that health selection could be contingent on people's social position as defined by gender and, thus, explain the gender differential in the relationship between unemployment and health. Ill people might be less reluctant to fall or remain (i.e., self-select) in unemployment if they have alternative roles. In Western societies, women generally have more alternative roles than men and thus more discretion in their labor market attachment. Therefore, health selection should be stronger for them, explaining why unemployment is less menace for women than for their male counterparts.
Finally, relying on the idea of different gender regimes, we extended these arguments to comparison across contexts. For example, in contexts where being a caregiver is assumed to be women's traditional and primary roles and the primary breadwinner role is reserved to men, unemployment is less stigmatized, and taking up alternative roles is more socially accepted for women than for men (Hp.1). Accordingly, social (self)selection should be stronger for women than for men in traditional contexts, where, in the case of ill-health, the separation from work is eased by the availability of alternative roles (Hp.2).
By focusing on contexts that are representative of different gender regimes, we implement a multiple-step comparative approach. Firstly, by using EU-SILC longitudinal data (2004-2015), our analysis tests gender roles and selection mechanisms for Sweden and Italy, representing radically different gender regimes, thus providing institutional and cultural variation. Then, we limit institutional heterogeneity by focusing on Germany and comparing East- and West-Germany and older and younger cohorts—for West-Germany (SOEP data 1995-2017). Next, to assess the differential impact of unemployment for men and women, we compared (unemployed and employed) men with (unemployed and employed) women. To do so, we calculate predicted probabilities and average marginal effect from two distinct random-effects probit models. Our first step is estimating random-effects models that assess the association between unemployment and self-perceived health, controlling for observable characteristics. In the second step, our fully adjusted model controls for both direct and indirect selection. We do this using dynamic correlated random-effects (CRE) models. Further, based on the fully adjusted model, we test our hypotheses on alternative roles (Hp.1) by comparing several contexts – models are estimated separately for each context. For this hypothesis, we pool men and women and include an interaction term between unemployment and gender, which has the advantage to allow for directly testing whether gender differences in the effect of unemployment exist and are statistically significant. Finally, we test the role of selection mechanisms (Hp.2), using the KHB method to compare coefficients across nested nonlinear models. Specifically, we test the role of selection for the relationship between unemployment and health by comparing the partially-adjusted and fully-adjusted models. To allow selection mechanisms to operate differently between genders, we estimate separate models for men and women.
We found support to our first hypotheses—the context where people are embedded structures the relationship between unemployment, health, and gender. We found no gendered effect of unemployment on health in the egalitarian context of Sweden. Conversely, in the traditional context of Italy, we observed substantive and statistically significant gender differences in the effect of unemployment on bad health, with women suffering less than men. We found the same pattern for comparing East and West Germany and younger and older cohorts in West Germany.
On the contrary, our results did not support our theoretical argument on social selection. We found that in Sweden, women are more selected out of employment than men. In contrast, in Italy, health selection does not seem to be the primary mechanism behind the gender differential—Italian men and women seem to be selected out of employment to the same extent. Namely, we do not find any evidence that health selection is stronger for women in more traditional countries (Hp2), despite the fact that the institutional and the cultural context would offer them a more comprehensive range of 'alternative roles' relative to men. Moreover, our second hypothesis is also rejected in the second and third comparisons, where the cross-country heterogeneity is reduced to maximize cultural differences within the same institutional context. Further research that addresses selection into inactivity is needed to evaluate the interplay between selection and social roles across gender regimes.
While the health consequences of unemployment have been on the research agenda for a pretty long time, the interest in precarious employment—defined as the linking of the vulnerable worker to work that is characterized by uncertainty and insecurity concerning pay, the stability of the work arrangement, limited access to social benefits, and statutory protections—has emerged only later. Since the 80s, scholars from different disciplines have raised concerns about the social consequences of de-standardization of employment relationships. However, while work has become undoubtedly more precarious, very little is known about its causal effect on individual health and the role of gender as a moderator. These questions are at the core of my third paper : 'Bad job, bad health? A longitudinal analysis of the interaction between precariousness, gender and self-perceived health in Germany'. Herein, I investigate the multidimensional nature of precarious employment and its causal effect on health, particularly focusing on gender differences.
With this paper, I aim at overcoming three major shortcomings of earlier studies: The first one regards the cross-sectional nature of data that prevents the authors from ruling out unobserved heterogeneity as a mechanism for the association between precarious employment and health. Indeed, several unmeasured individual characteristics—such as cognitive abilities—may confound the relationship between precarious work and health, leading to biased results. Secondly, only a few studies have directly addressed the role of gender in shaping the relationship. Moreover, available results on the gender differential are mixed and inconsistent: some found precarious employment being more detrimental for women's health, while others found no gender differences or stronger negative association for men. Finally, previous attempts to an empirical translation of the employment precariousness (EP) concept have not always been coherent with their theoretical framework. EP is usually assumed to be a multidimensional and continuous phenomenon; it is characterized by different dimensions of insecurity that may overlap in the same job and lead to different "degrees of precariousness." However, researchers have predominantly focused on one-dimensional indicators—e.g., temporary employment, subjective job insecurity—to measure EP and study the association with health. Besides the fact that this approach partially grasps the phenomenon's complexity, the major problem is the inconsistency of evidence that it has produced. Indeed, this line of inquiry generally reveals an ambiguous picture, with some studies finding substantial adverse effects of temporary over permanent employment, while others report only minor differences.
To measure the (causal) effect of precarious work on self-rated health and its variation by gender, I focus on Germany and use four waves from SOEP data (2003, 2007, 2011, and 2015). Germany is a suitable context for my study. Indeed, since the 1980s, the labor market and welfare system have been restructured in many ways to increase the German economy's competitiveness in the global market. As a result, the (standard) employment relationship has been de-standardized: non-standard and atypical employment arrangements—i.e., part-time work, fixed-term contracts, mini-jobs, and work agencies—have increased over time while wages have lowered, even among workers with standard work. In addition, the power of unions has also fallen over the last three decades, leaving a large share of workers without collective protection. Because of this process of de-standardization, the link between wage employment and strong social rights has eroded, making workers more powerless and more vulnerable to labor market risks than in the past. EP refers to this uneven distribution of power in the employment relationship, which can be detrimental to workers' health. Indeed, by affecting individuals' access to power and other resources, EP puts precarious workers at risk of experiencing health shocks and influences their ability to gain and accumulate health advantages (Hp.1).
Further, the focus on Germany allows me to investigate my second research question on the gender differential. Germany is usually regarded as a traditionalist gender regime: a context characterized by a configuration of roles. Here, being a caregiver is assumed to be women's primary role, whereas the primary breadwinner role is reserved for men. Although many signs of progress have been made over the last decades towards a greater equalization of opportunities and more egalitarianism, the breadwinner model has barely changed towards a modified version. Thus, women usually take on the double role of workers (the so-called secondary earner) and caregivers, and men still devote most of their time to paid work activities. Moreover, the overall upward trend towards more egalitarian gender ideologies has leveled off over the last decades, moving notably towards more traditional gender ideologies.
In this setting, two alternative hypotheses are possible. Firstly, I assume that the negative relationship between EP and health is stronger for women than for men. This is because women are systematically more disadvantaged than men in the public and private spheres of life, having less access to formal and informal sources of power. These gender-related power asymmetries may interact with EP-related power asymmetries resulting in a stronger effect of EP on women's health than on men's health (Hp.2).
An alternative way of looking at the gender differential is to consider the interaction that precariousness might have with men's and women's gender identities. According to this view, the negative relationship between EP and health is weaker for women than for men (Hp.2a). In a society with a gendered division of labor and a strong link between masculine identities and stable and well-rewarded job—i.e., a job that confers the role of primary family provider—a male worker with precarious employment might violate the traditional male gender role. Men in precarious jobs may perceive themselves (and by others) as possessing a socially undesirable characteristic, which conflicts with the stereotypical idea of themselves as the male breadwinner. Engaging in behaviors that contradict stereotypical gender identity may decrease self-esteem and foster feelings of inferiority, helplessness, and jealousy, leading to poor health.
I develop a new indicator of EP that empirically translates a definition of EP as a multidimensional and continuous phenomenon. I assume that EP is a latent construct composed of seven dimensions of insecurity chosen according to the theory and previous empirical research: Income insecurity, social insecurity, legal insecurity, employment insecurity, working-time insecurity, representation insecurity, worker's vulnerability. The seven dimensions are proxied by eight indicators available in the four waves of the SOEP dataset. The EP composite indicator is obtained by performing a multiple correspondence analysis (MCA) on the eight indicators. This approach aims to construct a summary scale in which all dimensions contribute jointly to the measured experience of precariousness and its health impact.
Further, the relationship between EP and 'general self-perceived health' is estimated by applying ordered probit random-effects estimators and calculating average marginal effect (further AME). Then, to control for unobserved heterogeneity, I implement correlated random-effects models that add to the model the within-individual means of the time-varying independent variables. To test the significance of the gender differential, I add an interaction term between EP and gender in the fully adjusted model in the pooled sample.
My correlated random-effects models showed EP's negative and substantial 'effect' on self-perceived health for both men and women. Although nonsignificant, the evidence seems in line with previous cross-sectional literature. It supports the hypothesis that employment precariousness could be detrimental to workers' health. Further, my results showed the crucial role of unobserved heterogeneity in shaping the health consequences of precarious employment. This is particularly important as evidence accumulates, yet it is still mostly descriptive.
Moreover, my results revealed a substantial difference among men and women in the relationship between EP and health: when EP increases, the risk of experiencing poor health increases much more for men than for women. This evidence falsifies previous theory according to whom the gender differential is contingent on the structurally disadvantaged position of women in western societies. In contrast, they seem to confirm the idea that men in precarious work could experience role conflict to a larger extent than women, as their self-standard is supposed to be the stereotypical breadwinner worker with a good and well-rewarded job. Finally, results from the multiple correspondence analysis contribute to the methodological debate on precariousness, showing that a multidimensional and continuous indicator can express a latent variable of EP.
All in all, complementarities are revealed in the results of unemployment and employment precariousness, which have two implications: Policy-makers need to be aware that the total costs of unemployment and precariousness go far beyond the economic and material realm penetrating other fundamental life domains such as individual health. Moreover, they need to balance the trade-off between protecting adequately unemployed people and fostering high-quality employment in reaction to the highlighted market pressures. In this sense, the further development of a (universalistic) welfare state certainly helps mitigate the adverse health effects of unemployment and, therefore, the future costs of both individuals' health and welfare spending. In addition, the presence of a working partner is crucial for reducing the health consequences of employment instability. Therefore, policies aiming to increase female labor market participation should be promoted, especially in those contexts where the welfare state is less developed.
Moreover, my results support the significance of taking account of a gender perspective in health research. The findings of the three articles show that job loss, unemployment, and precarious employment, in general, have adverse effects on men's health but less or absent consequences for women's health. Indeed, this suggests the importance of labor and health policies that consider and further distinguish the specific needs of the male and female labor force in Europe. Nevertheless, a further implication emerges: the health consequences of employment instability and de-standardization need to be investigated in light of the gender arrangements and the transforming gender relationships in specific cultural and institutional contexts. My results indeed seem to suggest that women's health advantage may be a transitory phenomenon, contingent on the predominant gendered institutional and cultural context. As the structural difference between men's and women's position in society is eroded, egalitarianism becomes the dominant normative status, so will probably be the gender difference in the health consequences of job loss and precariousness. Therefore, while gender equality in opportunities and roles is a desirable aspect for contemporary societies and a political goal that cannot be postponed further, this thesis raises a further and maybe more crucial question: What kind of equality should be pursued to provide men and women with both good life quality and equal chances in the public and private spheres? In this sense, I believe that social and labor policies aiming to reduce gender inequality in society should focus on improving women's integration into the labor market, implementing policies targeting men, and facilitating their involvement in the private sphere of life. Equal redistribution of social roles could activate a crucial transformation of gender roles and the cultural models that sustain and still legitimate gender inequality in Western societies.
Simultaneous Barcode Sequencing of Diverse Museum Collection Specimens Using a Mixed RNA Bait Set
(2022)
A growing number of publications presenting results from sequencing natural history collection specimens reflect the importance of DNA sequence information from such samples. Ancient DNA extraction and library preparation methods in combination with target gene capture are a way of unlocking archival DNA, including from formalin-fixed wet-collection material. Here we report on an experiment, in which we used an RNA bait set containing baits from a wide taxonomic range of species for DNA hybridisation capture of nuclear and mitochondrial targets for analysing natural history collection specimens. The bait set used consists of 2,492 mitochondrial and 530 nuclear RNA baits and comprises specific barcode loci of diverse animal groups including both invertebrates and vertebrates. The baits allowed to capture DNA sequence information of target barcode loci from 84% of the 37 samples tested, with nuclear markers being captured more frequently and consensus sequences of these being more complete compared to mitochondrial markers. Samples from dry material had a higher rate of success than wet-collection specimens, although target sequence information could be captured from 50% of formalin-fixed samples. Our study illustrates how efforts to obtain barcode sequence information from natural history collection specimens may be combined and are a way of implementing barcoding inventories of scientific collection material.
Objective: There is a lack of brief rating scales for the reliable assessment of psychotherapeutic skills, which do not require intensive rater training and/or a high level of expertise. Thus, the objective is to validate a 14-item version of the Clinical Communication Skills Scale (CCSS-S).
Methods: Using a sample of N = 690 video-based ratings of role-plays with simulated patients, we calculated a confirmatory factor analysis and an exploratory structural equation modeling (ESEM), assessed convergent validities, determined inter-rater reliabilities and compared these with those who were either psychology students, advanced psychotherapy trainees, or experts.
Results: Correlations with other competence rating scales were high (rs > 0.86–0.89). The intraclass correlations ranged between moderate and good [ICC(2,2) = 0.65–0.80], with student raters yielding the lowest scores. The one-factor model only marginally replicated the data, but the internal consistencies were excellent (α = 0.91–95). The ESEM yielded a two-factor solution (Collaboration and Structuring and Exploration Skills).
Conclusion: The CCSS-S is a brief and valid rating scale that reliably assesses basic communication skills, which is particularly useful for psychotherapy training using standardized role-plays. To ensure good inter-rater reliabilities, it is still advisable to employ raters with at least some clinical experience. Future studies should further investigate the one- or two-factor structure of the instrument.
The development of novel programmable materials aiming to control friction in real-time holds potential to facilitate innovative lubrication solutions for reducing wear and energy losses. This work describes the integration of light-responsiveness into two lubricating materials, silicon oils and polymer brush surfaces.
The first part focusses on the assessment on 9-anthracene ester-terminated polydimethylsiloxanes (PDMS-A) and, in particular, on the variability of rheological properties and the implications that arise with UV-light as external trigger. The applied rheometer setup contains an UV-transparent quartz-plate, which enables radiation and simultaneous measurement of the dynamic moduli. UV-A radiation (354 nm) triggers the cycloaddition reaction between the terminal functionalities of linear PDMS, resulting in chain extension. The newly-formed anthracene dimers cleave by UV-C radiation (254 nm) or at elevated temperatures (T > 130 °C). The sequential UV-A radiation and thermal reprogramming over three cycles demonstrate high conversions and reproducible programming of rheological properties. In contrast, the photochemical back reaction by UV-C is incomplete and can only partially restore the initial rheological properties. The dynamic moduli increase with each cycle in photochemical programming, presumably resulting from a chain segment re-arrangement as a result of the repeated partial photocleavage and subsequent chain length-dependent dimerization. In addition, long periods of radiation cause photooxidative degradation, which damages photo-responsive functions and consequently reduces the programming range. The absence of oxygen, however, reduces undesired side reactions. Anthracene-functionalized PDMS and native PDMS mix depending on the anthracene ester content and chain length, respectively, and allow fine-tuning of programmable rheological properties. The work shows the influence of mixing conditions during the photoprogramming step on the rheological properties, indicating that material property gradients induced by light attenuation along the beam have to be considered. Accordingly, thin lubricant films are suggested as potential application for light-programmable silicon fluids.
The second part compares strategies for the grafting of spiropyran (SP) containing copolymer brushes from Si wafers and evaluates the light-responsiveness of the surfaces. Pre-experiments on the kinetics of the thermally initiated RAFT copolymerization of 2-hydroxyethyl acrylate (HEA) and spiropyran acrylate (SPA) in solution show, first, a strong retardation by SP and, second, the dependence of SPA polymerization on light. Surprisingly, the copolymerization of SPA is inhibited in the dark. These findings contribute to improve the synthesis of polar, spiropyran-containing copolymers. The comparison between initiator systems for the grafting-from approach indicates PET-RAFT superior to thermally initiated RAFT, suggesting a more efficient initiation of surface-bound CTA by light. Surface-initiated polymerization via PET-RAFT with an initiator system of EosinY (EoY) and ascorbic acid (AscA) facilitates copolymer synthesis from HEA and 5-25 mol% SPA. The resulting polymer film with a thickness of a few nanometers was detected by atomic force microscopy (AFM) and ellipsometry. Water contact angle (CA) measurements demonstrate photo-switchable surface polarity, which is attributed to the photoisomerization between non-polar spiropyran and zwitterionic merocyanine isomer. Furthermore, the obtained spiropyran brushes show potential for further studies on light-programmable properties. In this context, it would be interesting to investigate whether swollen spiropyran-containing polymers change their configuration and thus their film thickness under the influence of light. In addition, further experiments using an AFM or microtribometer should evaluate whether light-programmable solvation enables a change in frictional properties between polymer brush surfaces.
Environmental pollution by microplastics has become a severe problem in terrestrial and aquatic ecosystems and, according to actual prognoses, problems will further increase in the future. Therefore, assessing and quantifying the risk for the biota is crucial. Standardized short-term toxicological procedures as well as methods quantifying potential toxic effects over the whole life span of an animal are required. We studied the effect of the microplastic polystyrene on the survival and reproduction of a common freshwater invertebrate, the rotifer Brachionus calyciflorus, at different timescales. We used pristine polystyrene spheres of 1, 3, and 6 µm diameter and fed them to the animals together with food algae in different ratios ranging from 0 to 50% nonfood particles. As a particle control, we used silica to distinguish between a pure particle effect and a plastic effect. After 24 h, no toxic effect was found, neither with polystyrene nor with silica. After 96 h, a toxic effect was detectable for both particle types. The size of the particles played a negligible role. Studying the long-term effect by using life table experiments, we found a reduced reproduction when the animals were fed with 3 µm spheres together with similar-sized food algae. We conclude that the fitness reduction is mainly driven by the dilution of food by the nonfood particles rather than by a direct toxic effect.
Pokhara (ca. 850 m a.s.l.), Nepal's second-largest city, lies at the foot of the Higher Himalayas and has more than tripled its population in the past 3 decades. Construction materials are in high demand in rapidly expanding built-up areas, and several informal settlements cater to unregulated sand and gravel mining in the Pokhara Valley's main river, the Seti Khola. This river is fed by the Sabche glacier below Annapurna III (7555 m a.s.l.), some 35 km upstream of the city, and traverses one of the steepest topographic gradients in the Himalayas. In May 2012 a sudden flood caused >70 fatalities and intense damage along this river and rekindled concerns about flood risk management. We estimate the flow dynamics and inundation depths of flood scenarios using the hydrodynamic model HEC-RAS (Hydrologic Engineering Center’s River Analysis System). We simulate the potential impacts of peak discharges from 1000 to 10 000 m3 s−1 on land cover based on high-resolution Maxar satellite imagery and OpenStreetMap data (buildings and road network). We also trace the dynamics of two informal settlements near Kaseri and Yamdi with high potential flood impact from RapidEye, PlanetScope, and Google Earth imagery of the past 2 decades. Our hydrodynamic simulations highlight several sites of potential hydraulic ponding that would largely affect these informal settlements and sites of sand and gravel mining. These built-up areas grew between 3- and 20-fold, thus likely raising local flood exposure well beyond changes in flood hazard. Besides these drastic local changes, about 1 % of Pokhara's built-up urban area and essential rural road network is in the highest-hazard zones highlighted by our flood simulations. Our results stress the need to adapt early-warning strategies for locally differing hydrological and geomorphic conditions in this rapidly growing urban watershed.
In this paper we examine the effect of uncertainty on readers’ predictions about meaning. In particular, we were interested in how uncertainty might influence the likelihood of committing to a specific sentence meaning. We conducted two event-related potential (ERP) experiments using particle verbs such as turn down and manipulated uncertainty by constraining the context such that readers could be either highly certain about the identity of a distant verb particle, such as turn the bed […] down, or less certain due to competing particles, such as turn the music […] up/down. The study was conducted in German, where verb particles appear clause-finally and may be separated from the verb by a large amount of material. We hypothesised that this separation would encourage readers to predict the particle, and that high certainty would make prediction of a specific particle more likely than lower certainty. If a specific particle was predicted, this would reflect a strong commitment to sentence meaning that should incur a higher processing cost if the prediction is wrong. If a specific particle was less likely to be predicted, commitment should be weaker and the processing cost of a wrong prediction lower. If true, this could suggest that uncertainty discourages predictions via an unacceptable cost-benefit ratio. However, given the clear predictions made by the literature, it was surprisingly unclear whether the uncertainty manipulation affected the two ERP components studied, the N400 and the PNP. Bayes factor analyses showed that evidence for our a priori hypothesised effect sizes was inconclusive, although there was decisive evidence against a priori hypothesised effect sizes larger than 1μV for the N400 and larger than 3μV for the PNP. We attribute the inconclusive finding to the properties of verb-particle dependencies that differ from the verb-noun dependencies in which the N400 and PNP are often studied.
Intuitively, strongly constraining contexts should lead to stronger probabilistic representations of sentences in memory. Encountering unexpected words could therefore be expected to trigger costlier shifts in these representations than expected words. However, psycholinguistic measures commonly used to study probabilistic processing, such as the N400 event-related potential (ERP) component, are sensitive to word predictability but not to contextual constraint. Some research suggests that constraint-related processing cost may be measurable via an ERP positivity following the N400, known as the anterior post-N400 positivity (PNP). The PNP is argued to reflect update of a sentence representation and to be distinct from the posterior P600, which reflects conflict detection and reanalysis. However, constraint-related PNP findings are inconsistent. We sought to conceptually replicate Federmeier et al. (2007) and Kuperberg et al. (2020), who observed that the PNP, but not the N400 or the P600, was affected by constraint at unexpected but plausible words. Using a pre-registered design and statistical approach maximising power, we demonstrated a dissociated effect of predictability and constraint: strong evidence for predictability but not constraint in the N400 window, and strong evidence for constraint but not predictability in the later window. However, the constraint effect was consistent with a P600 and not a PNP, suggesting increased conflict between a strong representation and unexpected input rather than greater update of the representation. We conclude that either a simple strong/weak constraint design is not always sufficient to elicit the PNP, or that previous PNP constraint findings could be an artifact of smaller sample size.
The key to reduce the energy required for specific transformations in a selective manner is the employment of a catalyst, a very small molecular platform that decides which type of energy to use. The field of photocatalysis exploits light energy to shape one type of molecules into others, more valuable and useful.
However, many challenges arise in this field, for example, catalysts employed usually are based on metal derivatives, which abundance is limited, they cannot be recycled and are expensive. Therefore, carbon nitrides materials are used in this work to expand horizons in the field of photocatalysis.
Carbon nitrides are organic materials, which can act as recyclable, cheap, non-toxic, heterogeneous photocatalysts. In this thesis, they have been exploited for the development of new catalytic methods, and shaped to develop new types of processes.
Indeed, they enabled the creation of a new photocatalytic synthetic strategy, the dichloromethylation of enones by dichloromethyl radical generated in situ from chloroform, a novel route for the making of building blocks to be used for the productions of active pharmaceutical compounds.
Then, the ductility of these materials allowed to shape carbon nitride into coating for lab vials, EPR capillaries, and a cell of a flow reactor showing the great potential of such flexible technology in photocatalysis.
Afterwards, their ability to store charges has been exploited in the reduction of organic substrates under dark conditions, gaining new insights regarding multisite proton coupled electron transfer processes.
Furthermore, the combination of carbon nitrides with flavins allowed the development of composite materials with improved photocatalytic activity in the CO2 photoreduction.
Concluding, carbon nitrides are a versatile class of photoactive materials, which may help to unveil further scientific discoveries and to develop a more sustainable future.
Creative thinking is an indispensable cognitive skill that is becoming increasingly important. In the present research, we tested the impact of games on creativity and emotions in a between-subject online experiment with four conditions (N = 658). (1) participants played a simple puzzle game that allowed many solutions (priming divergent thinking); (2) participants played a short game that required one fitting solution (priming convergent thinking); (3) participants performed mental arithmetic; (4) passive control condition. Results show that divergent and convergent creativity were higher after playing games and lower after mental arithmetic. Positive emotions did not function as a mediator, even though they were also heightened after playing the games and lower after mental arithmetic. However, contrary to previous research, we found no direct effect of emotions, creative self-efficacy, and growth- vs. fixed on creative performance. We discuss practical implications for digital learning and application settings.
Introduction: The ongoing COVID-19 pandemic situation caused by SARS-CoV-2 and variants of concern such as B.1.617.2 (Delta) and recently, B.1.1.529 (Omicron) is posing multiple challenges to humanity. The rapid evolution of the virus requires adaptation of diagnostic and therapeutic applications.
Objectives: In this study, we describe camelid heavy-chain-only antibodies (hcAb) as useful tools for novel in vitro diagnostic assays and for therapeutic applications due to their neutralizing capacity.
Methods: Five antibody candidates were selected out of a naïve camelid library by phage display and expressed as full length IgG2 antibodies. The antibodies were characterized by Western blot, enzyme-linked immunosorbent assays, surface plasmon resonance with regard to their specificity to the recombinant SARS-CoV-2 Spike protein and to SARS-CoV-2 virus-like particles. Neutralization assays were performed with authentic SARS-CoV-2 and pseudotyped viruses (wildtype and Omicron).
Results: All antibodies efficiently detect recombinant SARS-CoV-2 Spike protein and SARS-CoV-2 virus-like particles in different ELISA setups. The best combination was shown with hcAb B10 as catcher antibody and HRP-conjugated hcAb A7.2 as the detection antibody. Further, four out of five antibodies potently neutralized authentic wildtype SARS-CoV-2 and particles pseudotyped with the SARS-CoV-2 Spike proteins of the wildtype and Omicron variant, sublineage BA.1 at concentrations between 0.1 and 0.35 ng/mL (ND50).
Conclusion: Collectively, we report novel camelid hcAbs suitable for diagnostics and potential therapy.
The discovery that certain diseases have specific miRNA signatures which correspond to disease progression opens a new biomarker category. The detection of these small non-coding RNAs is performed routinely using body fluids or tissues with real-time PCR, next-generation sequencing, or amplification-based miRNA assays. Antibody-based detection systems allow an easy onset handling compared to PCR or sequencing and can be considered as alternative methods to support miRNA diagnostic in the future. In this study, we describe the generation of a camelid heavy-chain-only antibody specifically recognizing miRNAs to establish an antibody-based detection method. The generation of nucleic acid-specific binders is a challenge. We selected camelid binders via phage display, expressed them as VHH as well as full-length antibodies, and characterized the binding to several miRNAs from a signature specific for dilated cardiomyopathy. The described workflow can be used to create miRNA-specific binders and establish antibody-based detection methods to provide an additional way to analyze disease-specific miRNA signatures.
Genetic divergence and the frequency of hybridization are central for defining species delimitations, especially among cryptic species where morphological differences are merely absent. Rotifers are known for their high cryptic diversity and therefore are ideal model organisms to investigate such patterns. Here, we used the recently resolved Brachionus calyciflorus species complex to investigate whether previously observed between species differences in thermotolerance and gene expression are also reflected in their genomic footprint. We identified a Heat Shock Protein gene (HSP 40 kDa) which exhibits cross species pronounced sequence variation. This gene exhibits species-specific fixed sites, alleles, and sites putatively under positive selection. These sites are located in protein binding regions involved in chaperoning and may therefore reflect adaptive diversification. By comparing three genetic markers (ITS, COI, HSP 40 kDa), we revealed hybridization events between the cryptic species. The low frequency of introgressive haplotypes/alleles suggest a tight, but not fully impermeable boundary between the cryptic species.
Wheat alpha-amylase/trypsin inhibitors remain a subject of interest considering the latest findings showing their implication in wheat-related non-celiac sensitivity (NCWS). Understanding their functions in such a disorder is still unclear and for further study, the need for pure ATI molecules is one of the limiting problems. In this work, a simplified approach based on the successive fractionation of ATI extracts by reverse phase and ion exchange chromatography was developed. ATIs were first extracted from wheat flour using a combination of Tris buffer and chloroform/methanol methods. The separation of the extracts on a C18 column generated two main fractions of interest F1 and F2. The response surface methodology with the Doehlert design allowed optimizing the operating parameters of the strong anion exchange chromatography. Finally, the seven major wheat ATIs namely P01083, P17314, P16850, P01085, P16851, P16159, and P83207 were recovered with purity levels (according to the targeted LC-MS/MS analysis) of 98.2 ± 0.7; 98.1 ± 0.8; 97.9 ± 0.5; 95.1 ± 0.8; 98.3 ± 0.4; 96.9 ± 0.5, and 96.2 ± 0.4%, respectively. MALDI-TOF-MS analysis revealed single peaks in each of the pure fractions and the mass analysis yielded deviations of 0.4, 1.9, 0.1, 0.2, 0.2, 0.9, and 0.1% between the theoretical and the determined masses of P01083, P17314, P16850, P01085, P16851, P16159, and P83207, respectively. Overall, the study allowed establishing an efficient purification process of the most important wheat ATIs. This paves the way for further in-depth investigation of the ATIs to gain more knowledge related to their involvement in NCWS disease and to allow the absolute quantification in wheat samples.
This dataset comprises tree inventories and damage assessments performed in Namibia's semi-arid Zambezi Region. Data were sampled in savannas and savanna woodlands along steep gradients of elephant population densities to capture the effects of those (and other) disturbances on individual-level and stand-level aboveground woody biomass (AGB). The dataset contains raw data on dendrometric measures and processed data on specific wood density (SWD), woody aboveground biomass, and biomass losses through disturbance impacts. Allometric proxies (height, canopy diameters, and in adult trees also stem circumferences) were recorded for n = 6,179 tree and shrub individuals. Wood samples were taken for each encountered species to measure specific wood density.
These measurements have been used to estimate woody aboveground biomass via established allometric models, advanced through our improved methodologies and workflows that accounted for tree and shrub architecture shaped by disturbance impacts. To this end, we performed a detailed damage assessment on each woody individual in the field. In addition to estimations of standing biomass, our new method also delivered data on biomass losses to different disturbance agents (elephants, fire, and others) on the level of plant individuals and stands.
The data presented here have been used within a study published with Ecological Indicators (Kindermann et al., 2022) to evaluate the benefits of our improved methodology in comparison to a standard reference method of aboveground biomass estimations. Additionally, it has been employed in a study on carbon storage and sequestration in vegetation and soils (Sandhage-Hofmann et al., 2021).
The raw data of dendrometric measurements can be subjected to other available allometric models for biomass estimation. The processed data can be used to analyze disturbance impacts on woody aboveground biomass, or for regional carbon storage estimates. The data on species-specific wood density can be used for application to other dendrometric datasets to (re-) estimate biomass through allometric models requiring wood density. It can further be used for plant functional trait analyses.
Background
A growing body of literature is available regarding the effects of plyometric jump training (PJT) on measures of physical fitness (PF) and sport-specific performance (SSP) in-water sports athletes (WSA, i.e. those competing in sports that are practiced on [e.g. rowing] or in [e.g. swimming; water polo] water). Indeed, incoherent findings have been observed across individual studies making it difficult to provide the scientific community and coaches with consistent evidence. As such, a comprehensive systematic literature search should be conducted to clarify the existent evidence, identify the major gaps in the literature, and offer recommendations for future studies.
Aim
To examine the effects of PJT compared with active/specific-active controls on the PF (one-repetition maximum back squat strength, squat jump height, countermovement jump height, horizontal jump distance, body mass, fat mass, thigh girth) and SSP (in-water vertical jump, in-water agility, time trial) outcomes in WSA, through a systematic review with meta-analysis of randomized and non-randomized controlled studies.
Methods
The electronic databases PubMed, Scopus, and Web of Science were searched up to January 2022. According to the PICOS approach, the eligibility criteria were: (population) healthy WSA; (intervention) PJT interventions involving unilateral and/or bilateral jumps, and a minimal duration of ≥ 3 weeks; (comparator) active (i.e. standard sports training) or specific-active (i.e. alternative training intervention) control group(s); (outcome) at least one measure of PF (e.g. jump height) and/or SSP (e.g. time trial) before and after training; and (study design) multi-groups randomized and non-randomized controlled trials. The Physiotherapy Evidence Database (PEDro) scale was used to assess the methodological quality of the included studies. The DerSimonian and Laird random-effects model was used to compute the meta-analyses, reporting effect sizes (ES, i.e. Hedges’ g) with 95% confidence intervals (95% CIs). Statistical significance was set at p ≤ 0.05. Certainty or confidence in the body of evidence for each outcome was assessed using Grading of Recommendations Assessment, Development, and Evaluation (GRADE), considering its five dimensions: risk of bias in studies, indirectness, inconsistency, imprecision, and risk of publication bias.
Results
A total of 11,028 studies were identified with 26 considered eligible for inclusion. The median PEDro score across the included studies was 5.5 (moderate-to-high methodological quality). The included studies involved a total of 618 WSA of both sexes (330 participants in the intervention groups [31 groups] and 288 participants in the control groups [26 groups]), aged between 10 and 26 years, and from different sports disciplines such as swimming, triathlon, rowing, artistic swimming, and water polo. The duration of the training programmes in the intervention and control groups ranged from 4 to 36 weeks. The results of the meta-analysis indicated no effects of PJT compared to control conditions (including specific-active controls) for in-water vertical jump or agility (ES = − 0.15 to 0.03; p = 0.477 to 0.899), or for body mass, fat mass, and thigh girth (ES = 0.06 to 0.15; p = 0.452 to 0.841). In terms of measures of PF, moderate-to-large effects were noted in favour of the PJT groups compared to the control groups (including specific-active control groups) for one-repetition maximum back squat strength, horizontal jump distance, squat jump height, and countermovement jump height (ES = 0.67 to 1.47; p = 0.041 to < 0.001), in addition to a small effect noted in favour of the PJT for SSP time-trial speed (ES = 0.42; p = 0.005). Certainty of evidence across the included studies varied from very low-to-moderate.
Conclusions
PJT is more effective to improve measures of PF and SSP in WSA compared to control conditions involving traditional sport-specific training as well as alternative training interventions (e.g. resistance training). It is worth noting that the present findings are derived from 26 studies of moderate-to-high methodological quality, low-to-moderate impact of heterogeneity, and very low-to-moderate certainty of evidence based on GRADE.
Trial registration The protocol for this systematic review with meta-analysis was published in the Open Science platform (OSF) on January 23, 2022, under the registration doi https://doi.org/10.17605/OSF.IO/NWHS3 (internet archive link: https://archive.org/details/osf-registrations-nwhs3-v1).
Models are useful tools for understanding and predicting ecological patterns and processes. Under ongoing climate and biodiversity change, they can greatly facilitate decision-making in conservation and restoration and help designing adequate management strategies for an uncertain future. Here, we review the use of spatially explicit models for decision support and to identify key gaps in current modelling in conservation and restoration. Of 650 reviewed publications, 217 publications had a clear management application and were included in our quantitative analyses. Overall, modelling studies were biased towards static models (79%), towards the species and population level (80%) and towards conservation (rather than restoration) applications (71%). Correlative niche models were the most widely used model type. Dynamic models as well as the gene-to-individual level and the community-to-ecosystem level were underrepresented, and explicit cost optimisation approaches were only used in 10% of the studies. We present a new model typology for selecting models for animal conservation and restoration, characterising model types according to organisational levels, biological processes of interest and desired management applications. This typology will help to more closely link models to management goals. Additionally, future efforts need to overcome important challenges related to data integration, model integration and decision-making. We conclude with five key recommendations, suggesting that wider usage of spatially explicit models for decision support can be achieved by 1) developing a toolbox with multiple, easier-to-use methods, 2) improving calibration and validation of dynamic modelling approaches and 3) developing best-practise guidelines for applying these models. Further, more robust decision-making can be achieved by 4) combining multiple modelling approaches to assess uncertainty, and 5) placing models at the core of adaptive management. These efforts must be accompanied by long-term funding for modelling and monitoring, and improved communication between research and practise to ensure optimal conservation and restoration outcomes.
Background
Wearables, as small portable computer systems worn on the body, can track user fitness and health data, which can be used to customize health insurance contributions individually. In particular, insured individuals with a healthy lifestyle can receive a reduction of their contributions to be paid. However, this potential is hardly used in practice.
Objective
This study aims to identify which barrier factors impede the usage of wearables for assessing individual risk scores for health insurances, despite its technological feasibility, and to rank these barriers according to their relevance.
Methods
To reach these goals, we conduct a ranking-type Delphi study with the following three stages. First, we collected possible barrier factors from a panel of 16 experts and consolidated them to a list of 11 barrier categories. Second, the panel was asked to rank them regarding their relevance. Third, to enhance the panel consensus, the ranking was revealed to the experts, who were then asked to re-rank the barriers.
Results
The results suggest that regulation is the most important barrier. Other relevant barriers are false or inaccurate measurements and application errors caused by the users. Additionally, insurers could lack the required technological competence to use the wearable data appropriately.
Conclusion
A wider use of wearables and health apps could be achieved through regulatory modifications, especially regarding privacy issues. Even after assuring stricter regulations, users’ privacy concerns could partly remain, if the data exchange between wearables manufacturers, health app providers, and health insurers does not become more transparent.