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Conclusion
(2023)
Based on the previous findings in this book, Chapter 18 by Heike Krieger and Andrea Liese discusses the general dynamics of change or metamorphosis in the international legal order. They discern a mixed picture of an international order between metamorphosis—that is, a more fundamental transformation—of international law, norm change, turbulences, and robustness. They explain drivers of change and highlight factors such as national interests during the war on terror, changing long-term foreign policy beliefs, and the rise in populism and autocracy, before discussing the most common strategies the actors involved use. Other relevant factors include changes in the political environment, such as shocks and power shifts or the ambiguous role of fragmentation. Moreover, they identify factors that make legal norms robust, including the vital role of norm defenders and legal and institutional structures as stabilizing elements. Krieger and Liese conclude by cautioning that if the attacks on the international order continue at the current frequency and magnitude, a metamorphosis of international law will likely be unstoppable.
There is a growing recognition that international organizations (IOs) formulate and adopt policy in a wide range of areas. IOs have emerged as key venues for states seeking joint solutions to contemporary challenges such as climate change or COVID-19, and to establish frameworks to bolster trade, development, security, and more. In this capacity, IOs produce both extraordinary and routine policy output with a multitude of purposes, ranging from policies of historic significance like admitting new members to the more mundane tasks of administering IO staff. This article introduces the Intergovernmental Policy Output Dataset (IPOD), which covers close to 37,000 individual policy acts of 13 multi-issue IOs in the 1980–2015 period. The dataset fills a gap in the growing body of literature on the comparative study of IOs, providing researchers with a fine-grained perspective on the structure of IO policy output and data for comparisons across time, policy areas, and organizations. This article describes the construction and coverage of the dataset and identifies key temporal and cross-sectional patterns revealed by the data. In a concise illustration of the dataset’s utility, we apply models of punctuated equilibria in a comparative study of the relationship between institutional features and broad policy agenda dynamics. Overall, the Intergovernmental Policy Output Dataset offers a unique resource for researchers to analyze IO policy output in a granular manner and to explore questions of responsiveness, performance, and legitimacy of IOs.
When are international organizations (IOs) responsive to the policy problems that motivated their establishment? While it is a conventional assumption that IOs exist to address transnational challenges, the question of whether and when IO policy-making is responsive to shifts in underlying problems has not been systematically explored. This study investigates the responsiveness of IOs from a large-n, comparative approach. Theoretically, we develop three alternative models of IO responsiveness, emphasizing severeness, dependence, and power differentials. Empirically, we focus on the domain of security, examining the responsiveness of eight multi-issue IOs to armed conflict between 1980 and 2015, using a novel and expansive dataset on IO policy decisions. Our findings suggest, first, that IOs are responsive to security problems and, second, that responsiveness is not primarily driven by dependence or power differentials but by problem severity. An in-depth study of the responsiveness of the UN Security Council using more granular data confirms these findings. As the first comparative study of whether and when IO policy adapts to problem severity, the article has implications for debates about IO responsiveness, performance, and legitimacy.
The limitations and possibilities of the state in solving societal problems are perennial issues in the political and policy sciences and increasingly so in studies of environmental politics. With the aim of better understanding the role of the state in addressing environmental degradation through policy making, this article investigates the nexus between the environmental policy outputs and the environmental performance. Drawing on three theoretical perspectives on the state and market nexus in the environmental dilemma, we identify five distinct pathways. We then examine the extent to which these pathways are manifested in the real world. Our empirical investigation covers up to 37 countries for the period 1970–2010. While we see no global pattern of linkages between policy outputs and performance, our exploratory analysis finds evidence of policy effects, which suggest that the state can, under certain circumstances, improve the environment through policy making.
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.
The present thesis focuses on the synthesis of nanostructured iron-based compounds by using β-FeOOH nanospindles and poly(ionic liquid)s (PILs) vesicles as hard and soft templates, respectively, to suppress the shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. Three types of composites with different nanostructures (mesoporous nanospindle, yolk-shell nanospindle, and nanocapsule) have been synthesized and applied as sulfur host material for Li-S batteries. Their interactions with LiPSs and effects on the electrochemical performance of Li-S batteries have been systematically studied.
In the first part of the thesis, carbon-coated mesoporous Fe3O4 (C@M-Fe3O4) nanospindles have been synthesized to suppress the shuttle effect of LiPSs. First, β-FeOOH nanospindles have been synthesized via the hydrolysis of iron (III) chloride in aqueous solution and after silica coating and subsequent calcination, mesoporous Fe2O3 (M-Fe2O3) have been obtained inside the confined silica layer through pyrolysis of β-FeOOH. After the removal of the silica layer, electron tomography (ET) has been applied to rebuild the 3D structure of the M-Fe2O3 nanospindles. After coating a thin layer of polydopamine (PDA) as carbon source, the PDA-coated M-Fe2O3 particles have been calcinated to synthesize C@M-Fe3O4 nanospindles. With the chemisorption of Fe3O4 and confinement of mesoporous structure to anchor LiPSs, the composite C@M-Fe3O4/S electrode delivers a remaining capacity of 507.7 mAh g-1 at 1 C after 600 cycles.
In the second part of the thesis, a series of iron-based compounds (Fe3O4, FeS2, and FeS) with the same yolk-shell nanospindle morphology have been synthesized, which allows for the direct comparison of the effects of compositions on the electrochemical performance of Li-S batteries. The Fe3O4-carbon yolk-shell nanospindles have been synthesized by using the β-FeOOH nanospindles as hard template. Afterwards, Fe3O4-carbon yolk-shell nanospindles have been used as precursors to obtain iron sulfides (FeS and FeS2)-carbon yolk-shell nanospindles through sulfidation at different temperatures. Using the three types of yolk-shell nanospindles as sulfur host, the effects of compositions on interactions with LiPSs and electrochemical performance in Li-S batteries have been systematically investigated and compared. Benefiting from the chemisorption and catalytic effect of FeS2 particles and the physical confinement of the carbon shell, the FeS2-C/S electrode exhibits the best electrochemical performance with an initial specific discharge capacity of 877.6 mAh g-1 at 0.5 C and a retention ratio of 86.7% after 350 cycles.
In the third part, PILs vesicles have been used as soft template to synthesize carbon nanocapsules embedded with iron nitride particles to immobilize and catalyze LiPSs in Li-S batteries. First, 3-n-decyl-1-vinylimidazolium bromide has been used as monomer to synthesize PILs nanovesicles by free radical polymerization. Assisted by PDA coating route and ion exchange, PIL nanovesicles have been successfully applied as soft template in morphology-maintaining carbonization to prepare carbon nanocapsules embedded with iron nitride nanoparticles (FexN@C). The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electrical conductivity and strong chemical binding to LiPSs. The constructed FexN@C/S cathode demonstrates a high initial discharge capacity of 1085.0 mAh g-1 at 0.5 C with a remaining value of 930.0 mAh g-1 after 200 cycles.
The results in the present thesis demonstrate the facile synthetic routes of nanostructured iron-based compounds with controllable morphologies and compositions using soft and hard colloidal templates, which can be applied as sulfur host to suppress the shuttle behavior of LiPSs. The synthesis approaches developed in this thesis are also applicable to fabricating other transition metal-based compounds with porous nanostructures for other applications.
The present work focuses on the preparation and characterisation of various nanoplastic reference material candidates. Nanoplastics are plastic particles in a size range of 1 − 1000 nm. The term has emerged in recent years as a distinction from the larger microplastic (1 − 1000 μm). Since the properties of the two plastic particles differ significantly due to their size, it is important to have nanoplastic reference material. This was produced for the polymer types polypropylene (PP) and polyethylene (PE) as well as poly(lactic acid) (PLA).
A top-down method was used to produce the nanoplastic for the polyolefins PP and PE (Section 3.1). The material was crushed in acetone using an Ultra-Turrax disperser and then transferred to water. This process produces reproducible results when repeated, making it suitable for the production of a reference material candidate. The resulting dispersions were investigated using dynamic and electrophoretic light scattering. The dispersion of PP particles gave a mean hydrodynamic diameter Dh = 180.5±5.8 nm with a PDI = 0.08±0.02 and a zeta potential ζ = −43.0 ± 2.0 mV. For the PE particles, a diameter Dh = 344.5 ± 34.6 nm, with a PDI = 0.39 ± 0.04 and a zeta potential of ζ = −40.0 ± 4.2 mV was measured. This means that both dispersions are nanoplastics, as the particles are < 1000 nm. Furthermore, the starting material of these polyolefin particles was mixed with a gold salt and thereby the nanoplastic production was repeated in order to obtain nanoplastic particles doped with gold, which should simplify the detection of the particles.
In addition to the top-down approach, a bottom-up method was chosen for the PLA (Section 3.2). Here, the polymer was first dissolved in THF and stabilised with a surfactant. Then water was added and THF evaporated, leaving an aqueous PLA dispersion. This experiment was also investigated using dynamic light scattering and, when repeated, yielded reproducible results, i. e. an average hydrodynamic diameter of Dh = 89.2 ± 3.0 nm. Since the mass concentration of PLA in the dispersion is known due to the production method, a Python notebook was tested for these samples to calculate the number and mass concentration of nano(plastic) particles using the MALS results. Similar to the plastic produced in Section 3.1, gold was also incorporated into the particle, which was achieved by adding a dispersion of gold clusters with a diameter of D = 1.15 nm in an ionic liquid (IL) in the production process. Here, the preparation of the gold clusters in the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide ([Emim][DCA]) represented the first use of an IL both as a reducing agent for gold and as a solvent for the gold clusters. Two volumes of gold cluster dispersion were added during the PLA particle synthesis. The addition of the gold clusters leads to much larger particles. The nanoPLA with 0.8% Au has a diameter of Dh = 198.0 ± 10.8 nm and the nanoPLA with 4.9% Au has a diameter of Dh = 259.1 ± 23.7 nm. First investigations by TEM imaging show that the nanoPLA particles form hollow spheres when gold clusters are added. However, the mechanism leading to these structures remains unclear.
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.
The increasing global population has led to a growing demand for cost-effective and eco-friendly methods of water purification. This demand has reached a peak due to the increasing presence of impurities and pollutants in water and a growing awareness of waterborne diseases. Advanced oxidation processes (AOPs) are effective methods to address these challenges, due to the generation of highly reactive radicals, such as sulfate radical (SO4•-), hydroxyl radical (•OH), and/or superoxide radical (•O2-) in oxidation reactions. Relative to conventional hydrogen peroxide (H2O2)-based AOPs for wastewater treatment, the persulfate-related AOPs are receiving increasing attention over the past decades, due to their stronger oxidizing capability and a wider pH working window. Further deployment of the seemingly plausible technology as an alternative for the well-established one in industry, however, necessitates a careful evaluation of compounding factors, such as water matrix effects, toxicological consequences, costs, and engineering challenges, etc. To this end, rational design of efficient and environmentally friendly catalysts constitutes an indispensable pathway to advance persulfate activation efficacy and to elucidate the mechanisms in AOPs, the combined endeavors are expected to provide insightful understanding and guidelines for future studies in wastewater treatment. A dozens of transition metal-based catalysts have been developed for persulfate-related AOPs, while the undesirable metal leaching and poor stability in acidic conditions have been identified as major obstacles. Comparatively, the carbonaceous materials are emerging as alternative candidates, which are characterized by metal-free nature, wide availability, and exceptional resistance to acid and alkali, as well as tunable physicochemical and electronic properties, the combined merits make them an attractive option to overcome the aforementioned limitations in metal-based catalytic systems. This dissertation aims at developing novel carbonaceous materials to boost the activity in peroxymonosulfate (PMS) activation processes. Functionalized carbon materials with metal particles or heteroatoms were constructed and further evaluated in terms of their ability to activate PMS for AOPs. The main contents of this thesis are summarized as follows: (1) Iron oxide-loaded biochar: improving stability and alleviating metal leakage Metal leaching constitutes one of the main drawbacks in using transition metals as PMS activators, which is accompanied by the generation of metal-containing sludge, potentially leading to secondary pollution. Meanwhile, the metal nanoparticles are prone to aggregate, causing rapid decay of catalytic performance. The use of carbons as supports for transition metals could mitigate these deficiencies, because the interaction between metals and carbons could in turn disperse and stabilize metal nanoparticles, thus suppressing the metal leaching. In this work, the environmentally benign lignin with its abundant phenolic groups, which is well known to serve as carbon source with high yields and flexibility, was utilized to load Fe ions. The facile low-temperature pre-treatment pyrolytic strategy was employed to construct a green catalyst with iron oxides embedded in Kraft-lignin-derived biochar (termed as γ-Fe2O3@KC). The γ-Fe2O3@KC was capable of activating PMS to generate stable non-radical species (1O2 and Fe (V)=O) and to enhance electron transfer efficiency. A surface-bound reactive complex (catalyst-PMS*) was identified by electrochemical characterizations and discussed with primary surface-bound radical pairs to explain the contradictions between quenching and EPR detection results. The system also showed encouraging reusability for at least 5 times and high stability at pH 3-9. The low concentration of iron in γ-Fe2O3@KC/PMS system implied that the carbon scaffold of biochar substantially alleviated metal leakage. (2) MOF-derived nanocarbon: new carbon crystals Traditional carbon materials are of rather moderate performance in activation PMS, due to the poor electron transfer capacity within the amorphous structure and limited active sites for PMS adsorption. Herein, we established crystalline nanocarbon materials via a simple NaCl-templated strategy using the monoclinic zeolitic imidazolate framework-8 (ZIF-8) sealed with NaCl crystals as the precursors. Specifically, NaCl captured dual advantages in serving as structure-directing agent during hydrolysis and protective salt reactor to facilitate phase transformation during carbonization. The structure-directing agent NaCl provided a protective and confined space for the evolution of MOF upon carbonization, which led to high doping amounts of nitrogen (N) and oxygen elements (O) in carbon framework (N: 14.16 wt%, O: 9.6 wt%) after calcination at a high temperature of 950 oC. We found that N-O co-doping can activate the chemically inert carbon network and the nearby sp2-hybridized carbon atoms served as active sites for adsorption and activation. Besides, the highly crystallized structure with well-established carbon channels around activated carbon atoms could significantly accelerate electron transfer process after initial adsorption of PMS. As such, this crystalline nanocarbon exhibited excellent catalytic kinetics for various pollutants. (3) MOF-derived 2D carbon layers: enhanced mass/electron transfer The two-dimensional (2D) configuration of carbon-based nanosheets with inherent nanochannels and abundant active sites residing on the layer edges or in between the layers, allowed the accessible interaction and close contact between the substrates and reactants, as well as the dramatically improved electron- and mass-transfer kinetics. In this regard, we developed dual-templating strategy to afford 2D assembly of the crystalline carbons, which found efficiency in reinforcing the interactions between the catalyst surface and foreign pollutants. Specifically, we found that the ice crystals and NaCl promoted the evolution of MOF in a 2D fashion during the freezing casting stage, while the later further allowed the formation of a graphitic surface at high calcination temperature, by virtue of the templating effect of molten salt. Due to the highly retained co-doping amounts, N and O heteroatoms created abundant active sites for PMS activation, the 2D configuration of carbon-based nanosheets enable efficient interaction of PMS and pollutants on the surface, which further boosted the kinetics of degradation.
Consume-less appeals in social marketing can help reduce the lavish consumption in wealthy countries, which poses a major threat to the climate. This study experimentally examines the effectiveness of three different types of consume-less appeals (informative, social normative, and emotional appeals) on participants’ actual spending levels during a real shopping trip compared to a control group (no appeal). In addition, the study tests whether these appeals evoke negative rebounds (in terms of post-purchase climate donation) or positive rebounds (in terms of accepting post-purchase material giveaways). A field experiment in a grocery store in Germany with 170 participants shows that social normative and the emotional appeals reduce actual shopping spending. Informative and social normative appeals increase donations, and emotional appeals reduce the items of taken giveaways. The findings further support certain indirect impacts of the consume-less appeals on rebounds in terms of spending levels.
In the shadow of Valerian
(2023)
We live in an era driven by fossil fuels. The prevailing climate change suggests that we have to significantly reduce greenhouse gas emissions. The only way forward is to use renewable energy sources. Among those, solar energy is a clean, affordable, and sustainable source of energy. It has the potential to satisfy the world’s energy demand in the future. However, there is a need to develop new materials that can make solar energy usable. Photovoltaics (PV) are devices that convert photon energy into electrical energy. The most commonly used solar cells are based on crystalline silicon. However, the fabrication process for silicon solar cells is technologically difficult and costly. Solar cells based on lead halide perovskites (PSCs) have emerged as a new candidate for PV applications since 2009. To date, PSCs have achieved 26% power-conversion-efficiency (PCE) for its single junction, and 33.7% PCE for tandem junction devices. However, there is still room for improvement in overall performance. The main challenge for the commercialization of this technology is the stability of the solar cells under operational conditions. Inorganic perovskite CsPbI3 has attracted researchers’ interest due to its stability at elevated temperatures, however, inorganic perovskites also have associated challenges, e.g. phase stability, larger voltage loss compared to their organic-inorganic hybrid counterparts, and interface energy misalignment. The most efficient inorganic perovskite solar cell is stable for up to a few hundred hours while the most stable device in the field of inorganic PSCs reported so far is at 17% PCE. This suggests the need for improvement of the interfaces for enhanced open circuit voltage (VOC), and optimization of the energy alignment at the interfaces. This dissertation presents the study on interfaces between the perovskite layer and hole transport layer (HTL) for stable CsPbI3 solar cells.
The first part of the thesis presents an investigation of the CsPbI3 film annealing environment and its subsequent effects on the perovskite/HTL interface dynamics. Thin films annealed in dry air were compared with thin films annealed in ambient air. Synchrotron-based hard X-ray spectroscopy (HAXPES) measurements reveal that annealing in ambient air does not have an adverse effect; instead, those samples undergo surface band bending. This surface band modification induces changes in interface charge dynamics and, consequently, an improvement in charge extraction at the interfaces. Further, transient surface photovoltage (tr-SPV) simulations show that air-annealed samples exhibit fewer trap states compared to samples annealed in dry air. Finally, by annealing the CsPbI3 films in ambient air, a PCE of 19.8% and Voc of 1.23 V were achieved for an n-i-p structured device.
Interface engineering has emerged as a strategy to extract the charge and optimize the energy alignment in perovskite solar cells (PSCs). An interface with fewer trap states and energy band levels closer to the selective contact helps to attain improved efficiencies in PSCs. The second part of the thesis presents a design for the CsPbI3/HTM interface. In this work, an interface between CsPbI3 perovskite and its hole selective contact N2,N2,N2′,N2′,N7,N7,N7′,N7′-octakis(4-methoxyphenyl)-9,9′-spirobi[9H-fluorene]-2,2′,7,7′-tetramine(Spiro-OMeTAD), realized by trioctylphosphine oxide (TOPO), a dipole molecule is introduced. On top of a perovskite film well-passivated by n-octyl ammonium Iodide (OAI), it created an upward surface band-bending at the interface byTOPO that optimizes energy level alignment and enhances the extraction of holes from the perovskite layer to the hole transport material. Consequently, a Voc of 1.2 V and high-power conversion efficiency (PCE) of over 19% were achieved for inorganic CsPbI3 perovskite solar cells. In addition, the work also sheds light on the interfacial charge-selectivity and the long-term stability of CsPbI3 perovskite solar cells.
The third part of the thesis extends the previous studies to polymeric poly(3-hexylthiophene-2,5-diyl) (P3HT) as HTL. The CsPbI3/P3HT interface is critical due to high non-radiative recombination. This work presents a CsPbI3/P3HT interface modified with a long-chain alkyl halide molecule, n-hexyl trimethyl ammonium bromide (HTAB). This molecule largely passivates the CsPbI3 perovskite surface and improves the charge extraction across the interface. Consequently, a Voc of over 1.00 V and 14.2% PCE were achieved for CsPbI3 with P3HT as HTM.
Overall the results presented in this dissertation introduce and discuss methods to design and study the interfaces in CsPbI3-based solar cells. This study can pave the way for novel interface designs between CsPbI3 and HTM for charge extraction, efficiency and stability.
So Many Things are Yours
(2023)
The poet and Talmud scholar examines Jewish texts, sexuality, and human vulnerability in poems that brim with wonder, sadness, sensuality, and humor.
Kosman’s second volume in English explores Jewish texts ―Bible, Talmud, midrash ― alongside bodies, physical desires, military experiences, even a refrigerator. Demons and fantasy enter these poems; so do politics, so does God. These are not religious poems in a conventionally liturgical, “inspirational” sense; yet they point to the big questions that religion asks: about love, hate, desire, violence, transgression, disappointment.
Charitable giving
(2023)
We investigate how different levels of information influence the allocation decisions of donors who are entitled to freely distribute a fixed monetary endowment between themselves and a charitable organization in both giving and taking frames. Participants donate significantly higher amounts, when the decision is described as taking rather than giving. This framing effect becomes smaller if more information about the charity is provided.
Many phenomena of high relevance for economic development such as human capital, geography and climate vary considerably within countries as well as between them. Yet, global data sets of economic output are typically available at the national level only, thereby limiting the accuracy and precision of insights gained through empirical analyses. Recent work has used interpolation and downscaling to yield estimates of sub-national economic output at a global scale, but respective data sets based on official, reported values only are lacking. We here present DOSE — the MCC-PIK Database Of Sub-national Economic Output. DOSE contains harmonised data on reported economic output from 1,661 sub-national regions across 83 countries from 1960 to 2020. To avoid interpolation, values are assembled from numerous statistical agencies, yearbooks and the literature and harmonised for both aggregate and sectoral output. Moreover, we provide temporally- and spatially-consistent data for regional boundaries, enabling matching with geo-spatial data such as climate observations. DOSE provides the opportunity for detailed analyses of economic development at the subnational level, consistent with reported values.
Controlling bioenergy-induced land-use-change emissions is key to exploiting bioenergy for climate change mitigation. However, the effect of different land-use and energy sector policies on specific bioenergy emissions has not been studied so far. Using the global integrated assessment model REMIND-MAgPIE, we derive a biofuel emission factor (EF) for different policy frameworks. We find that a uniform price on emissions from both sectors keeps biofuel emissions at 12 kg CO2 GJ−1. However, without land-use regulation, the EF increases substantially (64 kg CO2 GJ−1 over 80 years, 92 kg CO2 GJ−1 over 30 years). We also find that comprehensive coverage (>90%) of carbon-rich land areas worldwide is key to containing land-use emissions. Pricing emissions indirectly on the level of bioenergy consumption reduces total emissions by cutting bioenergy demand but fails to reduce the average EF. In the absence of comprehensive and timely land-use regulation, bioenergy thus may contribute less to climate change mitigation than assumed previously.
Under current land-use regulation, carbon dioxide emissions from biofuel production exceed those from fossil diesel combustion. Therefore, international agreements need to ensure the effective and globally comprehensive protection of natural land before modern bioenergy can effectively contribute to achieving carbon neutrality.
Digital Platforms (DPs) has established themself in recent years as a central concept of the Information Technology Science. Due to the great diversity of digital platform concepts, clear definitions are still required. Furthermore, DPs are subject to dynamic changes from internal and external factors, which pose challenges for digital platform operators, developers and customers. Which current digital platform research directions should be taken to address these challenges remains open so far. The following paper aims to contribute to this by outlining a systematic literature review (SLR) on digital platform concepts in the context of the Industrial Internet of Things (IIoT) for manufacturing companies and provides a basis for (1) a selection of definitions of current digital platform and ecosystem concepts and (2) a selection of current digital platform research directions. These directions are diverted into (a) occurrence of digital platforms, (b) emergence of digital platforms, (c) evaluation of digital platforms, (d) development of digital platforms, and (e) selection of digital platforms.
Despite the merits of public and social media in private and professional spaces, citizens and professionals are increasingly exposed to cyberabuse, such as cyberbullying and hate speech. Thus, Law Enforcement Agencies (LEA) are deployed in many countries and organisations to enhance the preventive and reactive capabilities against cyberabuse. However, their tasks are getting more complex by the increasing amount and varying quality of information disseminated into public channels. Adopting the perspectives of Crisis Informatics and safety-critical Human-Computer Interaction (HCI) and based on both a narrative literature review and group discussions, this paper first outlines the research agenda of the CYLENCE project, which seeks to design strategies and tools for cross-media reporting, detection, and treatment of cyberbullying and hatespeech in investigative and law enforcement agencies. Second, it identifies and elaborates seven research challenges with regard to the monitoring, analysis and communication of cyberabuse in LEAs, which serve as a starting point for in-depth research within the project.
Working conditions of knowledge workers have been subject to rapid change recently. Digital nomadism is no longer a phenomenon that relates only to entrepreneurs, freelancers, and gig workers. Corporate employees, too, have begun to uncouple their work from stationary (home) offices and 9-to-5 schedules. However, pursuing a permanent job in a corporate environment is still subject to fundamentally different values than postulated by the original notion of digital nomadism. Therefore, this paper explores the work identity of what is referred to as ‘corporate nomads’. By drawing on identity theory and the results of semi-structured interviews, the paper proposes a conceptualization of the corporate nomad archetype and presents nine salient identity issues of corporate nomads (e.g., holding multiple contradictory identities, the flexibility paradox, or collaboration constraints). By introducing the ‘corporate nomad’ archetype to the Information Systems literature, this article helps to rethink established conceptions of “home office” and socio-spatial configurations of knowledge work.
In virtual collaboration at the workplace, a growing number of teams apply supportive conversational agents (CAs). They take on different work-related tasks for teams and single users such as scheduling meetings or stimulating creativity. Previous research merely focused on these positive aspects of introducing CAs at the workplace, omitting ethical challenges faced by teams using these often artificial intelligence (AI)-enabled technologies. Thus, on the one hand, CAs can present themselves as benevolent teammates, but on the other hand, they can collect user data, reduce worker autonomy, or foster social isolation by their service. In this work, we conducted 15 expert interviews with senior researchers from the fields of ethics, collaboration, and computer science in order to derive ethical guidelines for introducing CAs in virtual team collaboration. We derived 14 guidelines and seven research questions to pave the way for future research on the dark sides of human–agent interaction in organizations.
Digital transformation fundamentally changes the way individuals conduct work in organisations. In accordance with this statement, prevalent literature understands digital workplace transformation as a second-order effect of implementing new information technology to increase organisational effectiveness or reach other strategic goals. This paper, in contrast, provides empirical evidence from two remote-first organisations that undergo a proactive rather than reactive digital workplace transformation. The analysis of these cases suggests that new ways of working can be the consequence of an identity change that is a precondition for introducing new information technology rather than its outcome. The resulting process model contributes a competing argument to the existing debate in digital transformation literature. Instead of issuing digital workplace transformation as a deliverable of technological progress and strategic goals, this paper supports a notion of digital workplace transformation that serves a desired identity based on work preferences.
In this chapter, I consider the unity of self-consciousness and objectivity. Starting from the notion that the objective character and the self-conscious character of thought seem in tension, I discuss Sebastian Rödl’s Self-Consciousness and Objectivity and his thesis that this tension is merely apparent. This resolution suggests an immediate route to absolute idealism. I recall two Hegelian objections against such an immediate route. Against this background, it transpires that the dissolution of the apparent opposition of objectivity and self-consciousness can only be a preliminary step, opening our eyes to an actual opposition animating the pursuit of knowledge: the opposition of knowledge of nature and self-knowledge. This actual opposition cannot be removed as merely apparent and instead has to be sublated through articulation of its speculative unity. I consider two paradigms for the exposition of such a speculative unity: Kant’s account of judgments of beauty, and Hegel’s account of the speculative unity of life and self-consciousness. I close by contrasting these two approaches with Rödl’s characterization, which strikes me as one-sided. Absolute idealism, properly understood, requires us to develop the speculative unity of knowledge of nature and self-knowledge from both sides, showing us that knowledge of nature is self-knowledge, but equally: that self-knowledge requires knowledge of ourselves as nature.
The conception of property at the basis of Hegel’s conception of abstract right seems committed to a problematic form of “possessive individualism.” It seems to conceive of right as the expression of human mastery over nature and as based upon an irreducible opposition of person and nature, rightful will, and rightless thing. However, this chapter argues that Hegel starts with a form of possessive individualism only to show that it undermines itself. This is evident in the way Hegel unfolds the nature of property as it applies to external things as well as in the way he explains our self-ownership of our own bodies and lives. Hegel develops the idea of property to a point where it reaches a critical limit and encounters the “true right” that life possesses against the “formal” and “abstract right” of property. Ultimately, Hegel’s account suggests that nature should precisely not be treated as a rightless object at our arbitrary disposal but acknowledged as the inorganic body of right.
Intrinsic motivation is widely considered essential to creativity because it facilitates more divergent thinking during problem solving. However, we argue that intrinsic motivation has been theorized too heavily as a unitary construct, overlooking various internal factors of a task that can shape the baseline level of intrinsic motivation people have for working on the task. Drawing on theories of cognitive styles, we develop a new scale that measures individual preferences for three different creative thinking styles that we call divergent thinking, bricoleurgent thinking, and emergent thinking. Through a multi-study approach consisting of exploratory factor analysis, confirmatory factor analysis, and convergent validity, we provide psychometric evidence showing that people can have distinct preferences for each cognitive process when generating ideas. Furthermore, when validating this scale through an experiment, we find that each style becomes more dominant in predicting overall enjoyment, engagement, and creativity based on different underlying structures of a task. Therefore, this paper makes both theoretical and empirical contributions to literature by unpacking intrinsic motivation, showing how the alignment between different creative thinking styles and task can be essential to predicting intrinsic motivation, thus reversing the direction of causality between the motivational and cognitive components of creativity typically assumed in literature.
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.
The deformation style of mountain belts is greatly influenced by the upper plate architecture created during preceding deformation phases. The Mesozoic Salta Rift extensional phase has created a dominant structural and lithological framework that controls Cenozoic deformation and exhumation patterns in the Central Andes. Studying the nature of these pre-existing anisotropies is a key to understanding the spatiotemporal distribution of exhumation and its controlling factors. The Eastern Cordillera in particular, has a structural grain that is in part controlled by Salta Rift structures and their orientation relative to Andean shortening. As a result, there are areas in which Andean deformation prevails and areas where the influence of the Salta Rift is the main control on deformation patterns.
Between 23 and 24°S, lithological and structural heterogeneities imposed by the Lomas de Olmedo sub-basin (Salta Rift basin) affect the development of the Eastern Cordillera fold-and-thrust belt. The inverted northern margin of the sub-basin now forms the southern boundary of the intermontane Cianzo basin. The former western margin of the sub-basin is located at the confluence of the Subandean Zone, the Santa Barbara System and the Eastern Cordillera. Here, the Salta Rift basin architecture is responsible for the distribution of these morphotectonic provinces. In this study we use a multi-method approach consisting of low-temperature (U-Th-Sm)/He and apatite fission track thermochronology, detrital geochronology, structural and sedimentological analyses to investigate the Mesozoic structural inheritance of the Lomas de Olmedo sub-basin and Cenozoic exhumation patterns.
Characterization of the extension-related Tacurú Group as an intermediate succession between Paleozoic basement and the syn-rift infill of the Lomas de Olmedo sub-basin reveals a Jurassic maximum depositional age. Zircon (U-Th-Sm)/He cooling ages record a pre-Cretaceous onset of exhumation for the rift shoulders in the northern part of the sub-basin, whereas the western shoulder shows a more recent onset (140–115 Ma). Variations in the sedimentary thickness of syn- and post-rift strata document the evolution of accommodation space in the sub-basin. While the thickness of syn-rift strata increases rapidly toward the northern basin margin, the post-rift strata thickness decreases toward the margin and forms a condensed section on the rift shoulder.
Inversion of Salta Rift structures commenced between the late Oligocene and Miocene (24–15 Ma) in the ranges surrounding the Cianzo basin. The eastern and western limbs of the Cianzo syncline, located in the hanging wall of the basin-bounding Hornocal fault, show diachronous exhumation. At the same time, western fault blocks of Tilcara Range, south of the Cianzo basin, began exhuming in the late Oligocene to early Miocene (26–16 Ma). Eastward propagation to the frontal thrust and to the Paleozoic strata east of the Tilcara Range occurred in the middle Miocene (22–10 Ma) and the late Miocene–early Pliocene (10–4 Ma), respectively.
Traditional ways of reducing flood risk have encountered limitations in a climate-changing and rapidly urbanizing world. For instance, there has been a demanding requirement for massive investment in order to maintain a consistent level of security as well as increased flood exposure of people and property due to a false sense of security arising from the flood protection infrastructure. Against this background, nature-based solutions (NBS) have gained popularity as a sustainable and alternative way of dealing with diverse societal challenges such as climate change and biodiversity loss. In particular, their ability to reduce flood risks while also offering ecological benefits has recently received global attention. Diverse co-benefits of NBS that favor both humans and nature are viewed as promising a wide endorsement of NBS. However, people’s perceptions of NBS are not always positive. Local resistance to NBS projects as well as decision-makers’ and practitioners’ unwillingness to adopt NBS have been pointed out as a bottleneck to the successful realization and mainstreaming of NBS. In this regard, there has been a growing necessity to investigate people’s perceptions of NBS. Current research has lacked an integrative perspective of both attitudinal and contextual factors that guide perceptions of NBS; it not only lacks empirical evidence, but a few existing ones are rather conflicting without having underlying theories. This has led to the overarching research question of this dissertation, "What shapes people’s perceptions of NBS in the context of flooding?" The dissertation aims to answer the following sub-questions in the three papers that make up this dissertation: 1. What are the topics reflected in the previous literature influencing perceptions of NBS as a means to reduce hydro-meteorological risks? (Paper I) 2. What are the stimulating and hampering attitudinal and contextual factors for mainstreaming NBS for flood risk management? How are NBS conceptualized? (Paper II) 3. How are public attitudes toward the NBS projects shaped? How do risk-and place-related factors shape individual attitudes toward NBS? (Paper III) This dissertation follows an integrative approach of considering “place” and “risk”, as well as the surrounding context, by analyzing attitudinal (i.e., individual) and contextual (i.e., systemic) factors. “Place” is mainly concerned with affective elements (e.g., bond to locality and natural environment) whereas “risk” is related to cognitive elements (e.g., threat appraisal). The surrounding context provides systemic drivers and barriers with the possibility of interfering the influence of place and risk for perceptions of NBS. To empirically address the research questions, the current status of the knowledge about people’s perceptions of NBS for flood risks was investigated by conducting a systematic review (Paper I). Based on these insights, a case study of South Korea was used to demonstrate key contextual and attitudinal factors for mainstreaming NBS through the lens of experts (Paper II). Lastly, by conducting a citizen survey, it investigated the relationship between the previously discussed concepts in Papers I and II using structural equation modeling, focusing on the core concepts, namely risk and place (Paper III). As a result, Paper I identified the key topics relating to people’s perceptions, including the perceived value of co-benefits, perceived effectiveness of risk reduction effectiveness, participation of stakeholders, socio-economic and place-specific conditions, environmental attitude, and uncertainty of NBS. Paper II confirmed Paper I's findings regarding attitudinal factors. In addition, several contextual hampering or stimulating factors were found to be similar to those of any emerging technologies (i.e., path dependence, lack of operational and systemic capacity). Among all, one of the distinctive features in NBS contexts, at least in the South Korean case, is the politicization of NBS, which can lead to polarization of ideas and undermine the decision-making process. Finally, Paper III provides a framework with the core topics (i.e., place and risk) that were considered critical in Paper I and Paper II. This place-based risk appraisal model (PRAM) connects people at risk and places where hazards (i.e., floods) and interventions (i.e., NBS) take place. The empirical analysis shows that, among the place-related variables, nature bonding was a positive predictor of the perceived risk-reduction effectiveness of NBS, and place identity was a negative predictor of supportive attitude. Among the risk-related variables, threat appraisal had a negative effect on perceived risk reduction effectiveness and supportive attitude, while well-communicated information, trust in flood risk management, and perceived co-benefit were positive predictors. This dissertation proves that the place and risk attributes of NBS shape people’s perceptions of NBS. In order to optimize the NBS implementation, it is necessary to consider the meanings and values held in place before project implementation and how these attributes interact with individual and/or community risk profiles and other contextual factors. With the increasing necessity of using NBS to lower flood risks, these results make important suggestions for the future NBS project strategy and NBS governance.
Mountain ranges can fundamentally influence the physical and and chemical processes that shape Earths’ surface. With elevations of up to several kilometers they create climatic enclaves by interacting with atmospheric circulation and hydrologic systems, thus leading to a specific distribution of flora and fauna. As a result, the interiors of many Cenozoic mountain ranges are characterized by an arid climate, internally drained and sediment-filled basins, as well as unique ecosystems that are isolated from the adjacent humid, low-elevation regions along their flanks and forelands. These high-altitude interiors of orogens are often characterized by low relief and coalesced sedimentary basins, commonly referred to as plateaus, tectono-geomorphic entities that result from the complex interactions between mantle-driven geological and tectonic conditions and superposed atmospheric and hydrological processes. The efficiency of these processes and the fate of orogenic plateaus is therefore closely tied to the balance of constructive and destructive processes – tectonic uplift and erosion, respectively. In numerous geological studies it has been shown that mountain ranges are delicate systems that can be obliterated by an imbalance of these underlying forces. As such, Cenozoic mountain ranges might not persist on long geological timescales and will be destroyed by erosion or tectonic collapse. Advancing headward erosion of river systems that drain the flanks of the orogen may ultimately sever the internal drainage conditions and the maintenance of storage of sediments within the plateau, leading to destruction of plateau morphology and connectivity with the foreland. Orogenic collapse may be associated with the changeover from a compressional stress field with regional shortening and topographic growth, to a tensional stress field with regional extensional deformation and ensuing incision of the plateau. While the latter case is well-expressed by active extensional faults in the interior parts of the Tibetan Plateau and the Himalaya, for example, the former has been attributed to have breached the internally drained areas of the high-elevation sectors of the Iranian Plateau.
In the case of the Andes of South America and their internally drained Altiplano-Puna Plateau, signs of both processes have been previously described. However, in the orogenic collapse scenario the nature of the extensional structures had been primarily investigated in the northern and southern terminations of the plateau; in some cases, the extensional faults were even regarded to be inactive. After a shallow earthquake in 2020 within the Eastern Cordillera of Argentina that was associated with extensional deformation, the state of active deformation and the character of the stress field in the central parts of the plateau received renewed interest to explain a series of extensional structures in the northernmost sectors of the plateau in north-western Argentina. This study addresses (1) the issue of tectonic orogenic collapse of the Andes and the destruction of plateau morphology by studying the fill and erosion history of the central eastern Andean Plateau using sedimentological and geochronological data and (2) the kinematics, timing and magnitude of extensional structures that form well-expressed fault scarps in sediments of the regional San Juan del Oro surface, which is an integral part of the Andean Plateau and adjacent morphotectonic provinces to the east.
Importantly, sediment properties and depositional ages document that the San Juan del Oro Surface was not part of the internally-drained Andean Plateau, but rather associated with a foreland-directed drainage system, which was modified by the Andean orogeny and that became successively incorporated into the orogen by the eastward-migration of the Andean deformation front during late Miocene – Pliocene time. Structural and geomorphic observations within the plateau indicate that extensional processes must have been repeatedly active between the late Miocene and Holocene supporting the notion of plateau-wide extensional processes, potentially associated with Mw ~ 7 earthquakes. The close relationship between extensional joints and fault orientations underscores that 3 was oriented horizontally in NW-SE direction and 1 was vertical. This unambiguously documents that the observed deformation is related to gravitational forces that drive the orogenic collapse of the plateau. Applied geochronological analyses suggest that normal faulting in the northern Puna was active at about 3 Ma, based on paired cosmogenic nuclide dating of sediment fill units. Possibly due to regional normal faulting the drainage system within the plateau was modified, promoting fluvial incision.
Over the past decades, the traditional profile of the German administrative system has significantly been reshaped and remoulded through reforms and transformations. Manifold modernization efforts have been undertaken to adjust administrative structures and procedures to increasing challenges and pressures. In this chapter, the attempt is made to outline major institutional reform paths in Germany from Weberian bureaucracy to most recent reforms towards a digital transformation of public administration. We will show to what extent the German administrative system has moved away from the classical Weberian bureaucracy to a hybrid system where elements of the ‘old’ model and new reform paradigms such as the NPM and digital government are hybridized, labelled the Neo Weberian State. The question will be addressed as to what extent this shift has taken shape and which hurdles and path-dependencies can be identified to explain partial persistence and continuity over time.
As the climate targets tighten and countries are impacted by several crises, understanding how and under which conditions carbon dioxide emissions peak and start declining is gaining importance. We assess the timing of emissions peaks in all major emitters (1965–2019) and the extent to which past economic crises have impacted structural drivers of emissions contributing to emission peaks. We show that in 26 of 28 countries that have peaked emissions, the peak occurred just before or during a recession through the combined effect of lower economic growth (1.5 median percentage points per year) and decreasing energy and/or carbon intensity (0.7) during and after the crisis. In peak-and-decline countries, crises have typically magnified pre-existing improvements in structural change. In non-peaking countries, economic growth was less affected, and structural change effects were weaker or increased emissions. Crises do not automatically trigger peaks but may strengthen ongoing decarbonisation trends through several mechanisms.
Thermal energy from concentrating solar thermal technologies (CST) may contribute to decarbonizing applications from heating and cooling, desalination, and power generation to commodities such as aluminium, hydrogen, ammonia or sustainable aviation fuels (SAF). So far, successful commercial-scale CST projects are restricted to solar industrial process heat (SIPH) and concentrating solar power (CSP) generation and, at least for the latter, depend on support from public policies that have been stagnating for years. As they are technologically similar, spillovers between SIPH or CSP and other emerging CST could accelerate commercialization across use cases while maximizing the impact of scarce support. Here, we review the technical potential for cross-fertilization between different CST applications and the ability of the current policy regime to enable this potential. Using working temperature as the key variable, we identify different clusters of current and emerging CST technologies. Low-temperature CST (<400℃) applications for heating, cooling and desalination already profit from the significant progress made in line-focussing CSP over the last 15 years. A newly emerging cluster of high temperature CST (>600℃) for solar chemistry and high-grade process heat has significant leverage for spillovers with point-focussing solar tower third-generation CSP currently under development. For these spillovers to happen, however, CSP policy designs would need to prioritize innovation for high working temperature and encourage modular plant design, by adequately remunerating hybridized plants with heat and power in and outputs that include energy sources beyond CST solar fields. This would enable synergies across applications and scales by incentivizing compatibility of modular CST components in multiple sectors and use cases.
Renewable energy changes the geopolitics of energy: whereas access to fossil fuel resources were key in the past, control over technology and industry will be key in the future. Consequently, different scholars have predicted that a growing focus on renewables will increase or decrease conflict in the energy sector, with no consensus on which is most likely. Here, we investigate the degree of conflict in renewable energy technology (RET) trade by analyzing data on 7041 trade conflicts 1995–2020, guided by two sets of theory-driven hypotheses. We show that RET trade is associated with more, longer, and more intense trade conflicts than other trade conflicts for 1995–2016. This supports the neorealist, geo-economic view of countries being willing to risk conflict to increase their share of a market rather than avoiding conflicts to increase the overall market size. It also contradicts the view that renewables will reduce conflict: at least in the past and regarding trade, it has increased rather than decreased conflict. For 2017–2020, this trend is reversed and RET trade became significantly less conflictive than other trade. Our findings imply that improved conflict-resolution institutions for RET are needed. We also suggest establishing specific institutions to govern trade in immature technologies.
SNS Democracy Council 2023
(2023)
Transboundary problems such as climate change, military conflicts, trade barriers, and refugee flows require increased collaboration across borders. This is to a large extent possible using existing international organizations. In such a case, however, they need to be considerably strengthened – while current trends take us in the opposite direction, according to the researchers in the SNS Democracy Council 2023.
Sulfur is essential for the functionality of some important biomolecules in humans. Biomolecules like the Iron-sulfur clusters, tRNAs, Molybdenum cofactor, and some vitamins. The trafficking of sulfur involves proteins collectively called sulfurtransferase. Among these are TUM1, MOCS3, and NFS1.
This research investigated the role of TUM1 for molybdenum cofactor biosynthesis and cytosolic tRNA thiolation in humans. The rhodanese-like protein MOCS3 and the L-cysteine desulfurase (NFS1) have been previously demonstrated to interact with TUM1. These interactions suggested a dual function of TUM1 in sulfur transfer for Moco biosynthesis and cytosolic tRNA thiolation. TUM1 deficiency has been implicated to be responsible for a rare inheritable disorder known as mercaptolactate cysteine disulfiduria (MCDU), which is associated with a mental disorder. This mental disorder is similar to the symptoms of sulfite oxidase deficiency which is characterised by neurological disorders. Therefore, the role of TUM1 as a sulfurtransferase in humans was investigated, in CRISPR/Cas9 generated TUM1 knockout HEK 293T cell lines.
For the first time, TUM1 was implicated in Moco biosynthesis in humans by quantifying the intermediate product cPMP and Moco using HPLC. Comparing the TUM1 knockout cell lines to the wild-type, accumulation and reduction of cPMP and Moco were observed respectively. The effect of TUM1 knockout on the activity of a Moco-dependent enzyme, Sulfite oxidase, was also investigated. Sulfite oxidase is essential for the detoxification of sulfite to sulfate. Sulfite oxidase activity and protein abundance were reduced due to less availability of Moco. This shows that TUM1 is essential for efficient sulfur transfer for Moco biosynthesis. Reduction in cystathionin -lyase in TUM1 knockout cells was quantified, a possible coping mechanism of the cell against sulfite production through cysteine catabolism.
Secondly, the involvement of TUM1 in tRNA thio-modification at the wobble Uridine-34 was reported by quantifying the amount of mcm5s2U and mcm5U via HPLC. The reduction and accumulation of mcm5s2U and mcm5U in TUM1 knockout cells were observed in the nucleoside analysis. Herein, exogenous treatment with NaHS, a hydrogen sulfide donor, rescued the Moco biosynthesis, cytosolic tRNA thiolation, and cell proliferation deficits in TUM1 knockout cells.
Further, TUM1 was shown to impact mitochondria bioenergetics through the measurement of the oxygen consumption rate and extracellular acidification rate (ECAR) via the seahorse cell Mito stress analyzer. Reduction in total ATP production was also measured. This reveals how important TUM1 is for H2S biosynthesis in the mitochondria of HEK 293T.
Finally, the inhibition of NFS1 in HEK 293T and purified NFS1 protein by 2-methylene 3-quinuclidinone was demonstrated via spectrophotometric and radioactivity quantification. Inhibition of NFS1 by MQ further affected the iron-sulfur cluster-dependent enzyme aconitase activity.
Point processes are a common methodology to model sets of events. From earthquakes to social media posts, from the arrival times of neuronal spikes to the timing of crimes, from stock prices to disease spreading -- these phenomena can be reduced to the occurrences of events concentrated in points. Often, these events happen one after the other defining a time--series.
Models of point processes can be used to deepen our understanding of such events and for classification and prediction. Such models include an underlying random process that generates the events. This work uses Bayesian methodology to infer the underlying generative process from observed data. Our contribution is twofold -- we develop new models and new inference methods for these processes.
We propose a model that extends the family of point processes where the occurrence of an event depends on the previous events. This family is known as Hawkes processes. Whereas in most existing models of such processes, past events are assumed to have only an excitatory effect on future events, we focus on the newly developed nonlinear Hawkes process, where past events could have excitatory and inhibitory effects. After defining the model, we present its inference method and apply it to data from different fields, among others, to neuronal activity.
The second model described in the thesis concerns a specific instance of point processes --- the decision process underlying human gaze control. This process results in a series of fixated locations in an image. We developed a new model to describe this process, motivated by the known Exploration--Exploitation dilemma. Alongside the model, we present a Bayesian inference algorithm to infer the model parameters.
Remaining in the realm of human scene viewing, we identify the lack of best practices for Bayesian inference in this field. We survey four popular algorithms and compare their performances for parameter inference in two scan path models.
The novel models and inference algorithms presented in this dissertation enrich the understanding of point process data and allow us to uncover meaningful insights.
Lanthanide based ceria nanomaterials are important practical materials due to their redox properties that are useful in technology and life sciences. This PhD thesis examined various properties and potential for catalytic and bio-applications of Ln3+-doped ceria nanomaterials. Ce1-xGdxO2-y: Eu3+, gadolinium doped ceria (GDC) (0 ≤ x ≤ 0.4) nanoparticles were synthesized by flame spray pyrolysis (FSP) and studied, followed by 15 % CexZr1-xO2-y: Eu3+|YSZ (0 ≤ x ≤ 1) nanocomposites. Furthermore, Ce1-xYb xO2-y (0.004 ≤ x ≤ 0.22) nanoparticles were synthesized by thermal decomposition and characterized. Finally, CeO2-y: Eu3+ nanoparticles were synthesized by a microemulsion method, biofunctionalized and characterized. The studies undertaken presents a novel approach to structurally elucidate ceria-based nanomaterials by way of Eu3+ and Yb3+ spectroscopy and processing the spectroscopic data with the multi-way decomposition method PARAFAC. Data sets of the three variables: excitation wavelength, emission wavelength and time were used to perform the deconvolution of spectra.
GDC nanoparticles from FSP are nano-sized and of roughly cubic shape and crystal structure (Fm3̅m). Raman data revealed four vibrational modes exhibited by Gd3+ containing samples whereas CeO2-y: Eu3+ displays only two. The room temperature, time-resolved emission spectra recorded at λexcitation = 464 nm show that Gd3+ doping results in significantly altered emission spectra compared to pure ceria. The PARAFAC analysis for the pure ceria samples reveals two species; a high-symmetry species and a low-symmetry species. The GDC samples yield two low-symmetry spectra in the same experiment. High-resolution emission spectra recorded at 4 K after probing the 5D0-7F0 transition revealed additional variation in the low symmetry Eu3+ sites in pure ceria and GDC. The data of the Gd3+-containing samples indicates that the average charge density around the Eu3+ ions in the lattice is inversely related to Gd3+ and oxygen vacancy concentration.
The particle crystallites of the 773 K and 1273 K annealed Yb3+ -ceria nanostructure materials are nano-sized and have a cubic fluorite structure with four Raman vibrational modes. Elemental maps clearly show that cluster formation occurs for 773 K annealed with high Yb3+ ion concentration from 15 mol % in the ceria lattice. These clusters are destroyed with annealing to 1273 K. The emission spectra observed from room temperature and 4 K measurements for the Ce1-xYb xO2-y samples have a manifold that corresponds to the 2F5/2-2F7/2 transition of Yb3+ ions. Some small shifts are observed in the Stark splitting pattern and are induced by the variations of the crystal field influenced by where the Yb3+ ions are located in the crystal lattices in the samples. Upon mixing ceria with high Yb3+ concentrations, the 2F5/2-2F7/2 transition is also observed in the Stark splitting pattern, but the spectra consist of two broad high background dominated peaks. Annealing the nanomaterials at 1273 K for 2 h changes the spectral signature as new peaks emerge. The deconvolution yielded luminescence decay kinetics as well as the accompanying luminescence spectra of three species for each of the low Yb3+ doped ceria samples annealed at 773 K and one species for the 1273 K annealed samples. However, the ceria samples with high Yb3+ concentration annealed at the two temperatures yielded one species with lower decay times as compared to the Yb3+ doped ceria samples after PARAFAC analysis.
Through the calcination of the nanocomposites at two high temperatures, the evolution of the emission patterns from specific Eu3+ lattice sites to indicate structural changes for the nanocomposites was followed. The spectroscopy results effectively complemented the data obtained from the conventional techniques. Annealing the samples at 773 K, resulted in amorphous, unordered domains whereas the TLS of the 1273 K nanocomposites reveal two distinct sites, with most red shifted Eu3+ species coming from pure Eu3+ doped ZrO2 on the YSZ support.
Finally, for Eu3+ doped ceria, successful transfer from hydrophobic to water phase and subsequent biocompatibility was achieved using ssDNA. PARAFAC analysis for the Eu3+ in nanoparticles dispersed in toluene and water revealed one Eu3+ species, with slightly differing surface properties for the nanoparticles as far as the luminescence kinetics and solvent environments were concerned. Several functionalized nanoparticles conjugated onto origami triangles after hybridization were visualized by atomic force microscopy (AFM). Putting all into consideration, Eu3+ and Yb3+ spectroscopy was used to monitor the structural changes and determining the feasibility of the nanoparticle transfer into water. PARAFAC proves to be a powerful tool to analyze lanthanide spectra in crystalline solid materials and in solutions, which are characterized by numerous Stark transitions and where measurements usually yield a superposition of different emission contributions to any given spectrum.
Economic agents often irrationally base their decision-making on irrelevant information. This research analyzes whether men and women react to futile information about past outcomes. For this purpose, we run a laboratory experiment (Study 1) and use field data (Study 2). In both studies, the behavior of men is consistent with falsely assumed negative autocorrelation, often referred to as gambler’s fallacy Women’s behavior aligns with falsely assumed positive autocorrelation, a notion of the hot hand fallacy. On the aggregate, the two fallacies cancel out. Even when individuals are, on average, rational, the biases in the decision-making of subgroups might cause inefficient outcomes. In a mediation analysis, we find that a) the agents stated perceived probabilities of future outcomes are not blurred by irrelevant information and b) about 40 % of the observed biases are driven by differences in the perceived attractiveness of available choices caused by the irrelevant information.
Labor unions’ greatest potential for political influence likely arises from their direct connection to millions of individuals at the workplace. There, they may change the ideological positions of both unionizing workers and their non-unionizing management. In this paper, we analyze the workplace-level impact of unionization on workers’ and managers’ political campaign contributions over the 1980-2016 period in the United States. To do so, we link establishment-level union election data with transaction-level campaign contributions to federal and local candidates. In a difference-in-differences design that we validate with regression discontinuity tests and a novel instrumental variables approach, we find that unionization leads to a leftward shift of campaign contributions. Unionization increases the support for Democrats relative to Republicans not only among workers but also among managers, which speaks against an increase in political cleavages between the two groups. We provide evidence that our results are not driven by compositional changes of the workforce and are weaker in states with Right-to-Work laws where unions can invest fewer resources in political activities.
RailChain
(2023)
The RailChain project designed, implemented, and experimentally evaluated a juridical recorder that is based on a distributed consensus protocol. That juridical blockchain recorder has been realized as distributed ledger on board the advanced TrainLab (ICE-TD 605 017) of Deutsche Bahn.
For the project, a consortium consisting of DB Systel, Siemens, Siemens Mobility, the Hasso Plattner Institute for Digital Engineering, Technische Universität Braunschweig, TÜV Rheinland InterTraffic, and Spherity has been formed. These partners not only concentrated competencies in railway operation, computer science, regulation, and approval, but also combined experiences from industry, research from academia, and enthusiasm from startups.
Distributed ledger technologies (DLTs) define distributed databases and express a digital protocol for transactions between business partners without the need for a trusted intermediary. The implementation of a blockchain with real-time requirements for the local network of a railway system (e.g., interlocking or train) allows to log data in the distributed system verifiably in real-time. For this, railway-specific assumptions can be leveraged to make modifications to standard blockchains protocols.
EULYNX and OCORA (Open CCS On-board Reference Architecture) are parts of a future European reference architecture for control command and signalling (CCS, Reference CCS Architecture – RCA). Both architectural concepts outline heterogeneous IT systems with components from multiple manufacturers. Such systems introduce novel challenges for the approved and safety-relevant CCS of railways which were considered neither for road-side nor for on-board systems so far. Logging implementations, such as the common juridical recorder on vehicles, can no longer be realized as a central component of a single manufacturer. All centralized approaches are in question.
The research project RailChain is funded by the mFUND program and gives practical evidence that distributed consensus protocols are a proper means to immutably (for legal purposes) store state information of many system components from multiple manufacturers. The results of RailChain have been published, prototypically implemented, and experimentally evaluated in large-scale field tests on the advanced TrainLab. At the same time, the project showed how RailChain can be integrated into the road-side and on-board architecture given by OCORA and EULYNX.
Logged data can now be analysed sooner and also their trustworthiness is being increased. This enables, e.g., auditable predictive maintenance, because it is ensured that data is authentic and unmodified at any point in time.
Interested in the ideological workings of fiction, I study how major avant-garde tropes promote the potential of permanent renewal as white America’s property. Renewal ties to the capacities to create, progress, transcend, and simply be. From Black critique we know that, within dominant discourse, all these capacities have been denied to Black bodies ever since colonization. Black work has been fetishized, appropriated, stolen, and dismissed in and by dominant culture, while Black being is construed as negativity and barred on the level of ontology. It follows then that racialization operates on multiple levels in the conceptual frame of renewal. I study this conceptualization by re-reading the works of and criticism on progressive white authors. I examine how images of renewal enable the claim on futurity, transformative potential, and movement forward as exclusively white properties. Premised on oppositions between positive capacities and a state of complete incapacitation, these images are often viewed as separate constructions. This project shows that, deriving from white ideology, such representations are symbiotic and simultaneous - the "good" story of white renewal rests on the continual transgression towards Black being.
Spring Issue
(2023)
Biofilms are heterogeneous structures made of microorganisms embedded in a self-secreted extracellular matrix. Recently, biofilms have been studied as sustainable living materials with a focus on the tuning of their mechanical properties. One way of doing so is to use metal ions. In particular biofilms have been shown to stiffen in presence of some metal cations and to soften in presence of others. However, the specificity and the determinants of those interactions vary between species. While Escherichia coli is a widely studied model organism, little is known concerning the response of its biofilms to metal ions. In this work, we aimed at tuning the mechanics of E. coli biofilms by acting on the interplay between matrix composition and metal cations. To do so, we worked with E. coli strains producing a matrix composed of curli amyloid fibres or phosphoethanolamine-cellulose (pEtN-cellulose) fibres or both. The viscoelastic behaviour of the resulting biofilms was investigated with rheology after incubation with one of the following metal ion solutions: FeCl3, AlCl3, ZnCl2 and CaCl2 or ultrapure water. We observed that the strain producing both fibres stiffen by a factor of two when exposed to the trivalent metal cations Al(III) and Fe(III) while no such response is observed for the bivalent cations Zn(II) and Ca(II). Strains producing only one matrix component did not show any stiffening in response to either cation, but even a small softening. In order to investigate further the contribution of each matrix component to the mechanical properties, we introduced additional bacterial strains producing curli fibres in combination with non-modified cellulose, non-modified cellulose only or neither component. We measured biofilms produced by those different strains with rheology and without any solution. Since rheology does not preserve the architecture of the matrix, we compared those results to the mechanical properties of biofilms probed with the non-destructive microindentation. The microindentation results showed that biofilm stiffness is mainly determined by the presence of curli amyloid fibres in the matrix. However, this clear distinction between biofilm matrices containing or not containing curli is absent from the rheology results, i.e. following partial destruction of the matrix architecture. In addition, rheology also indicated a negative impact of curli on biofilm yield stress and flow stress. This suggests that curli fibres are more brittle and therefore more affected by the mechanical treatments. Finally, to examine the molecular interactions between the biofilms and the metal cations, we used Attenuated total reflectance - Fourier transform infrared spectroscopy (ATR-FTIR) to study the three E.coli strains producing a matrix composed of curli amyloid fibres, pEtN-cellulose fibres or both. We measured biofilms produced by those strains in presence of each of the aforementioned metal cation solutions or ultrapure water. We showed that the three strains cannot be distinguished based on their FTIR spectra and that metal cations seem to have a non-specific effect on bacterial membranes in absence of pEtN-cellulose. We subsequently conducted similar experiments on purified curli or pEtN-cellulose fibres. The spectra of the pEtN-cellulose fibres revealed a non-valence-specific interaction between metal cations and the phosphate of the pEtN-modification. Altogether, these results demonstrate that the mechanical properties of E. coli biofilms can be tuned via incubation with metal ions. While the mechanism involving curli fibres remains to be determined, metal cations seem to adsorb onto pEtN-cellulose and this is not valence-specific. This work also underlines the importance of matrix architecture to biofilm mechanics and emphasises the specificity of each matrix composition.