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Institute
- Extern (428)
- Institut für Physik und Astronomie (41)
- Institut für Geowissenschaften (37)
- Center for Economic Policy Analysis (CEPA) (32)
- Institut für Chemie (30)
- Fachgruppe Volkswirtschaftslehre (27)
- Vereinigung für Jüdische Studien e. V. (23)
- Institut für Biochemie und Biologie (19)
- Department Psychologie (17)
- Department Linguistik (16)
Both horizontal-to-vertical (H/V) spectral ratios and the spatial autocorrelation method (SPAC) have proven to be valuable tools to gain insight into local site effects by ambient noise measurements. Here, the two methods are employed to assess the subsurface velocity structure at the Piano delle Concazze area on Mt Etna. Volcanic tremor records from an array of 26 broadband seismometers is processed and a strong variability of H/V ratios during periods of increased volcanic activity is found. From the spatial distribution of H/V peak frequencies, a geologic structure in the north-east of Piano delle Concazze is imaged which is interpreted as the Ellittico caldera rim. The method is extended to include both velocity data from the broadband stations and distributed acoustic sensing data from a co-located 1.5 km long fibre optic cable. High maximum amplitude values of the resulting ratios along the trajectory of the cable coincide with known faults. The outcome also indicates previously unmapped parts of a fault. The geologic interpretation is in good agreement with inversion results from magnetic survey data. Using the neighborhood algorithm, spatial autocorrelation curves obtained from the modified SPAC are inverted alone and jointly with the H/V peak frequencies for 1D shear wave velocity profiles. The obtained models are largely consistent with published models and were able to validate the results from the fibre optic cable.
Reactive eutectic media based on ammonium formate for the valorization of bio-sourced materials
(2023)
In the last several decades eutectic mixtures of different compositions were successfully used as solvents for vast amount of chemical processes, and only relatively recently they were discovered to be widely spread in nature. As such they are discussed as a third liquid media of the living cell, that is composed of common cell metabolites. Such media may also incorporate water as a eutectic component in order to regulate properties such as enzyme activity or viscosity. Taking inspiration form such sophisticated use of eutectic mixtures, this thesis will explore the use of reactive eutectic media (REM) for organic synthesis. Such unconventional media are characterized by the reactivity of their components, which means that mixture may assume the role of the solvent as well as the reactant itself.
The thesis focuses on novel REM based on ammonium formate and investigates their potential for the valorization of bio-sourced materials. The use of REM allows the performance of a number of solvent-free reactions, which entails the benefits of a superior atom and energy economy, higher yields and faster rates compared to reactions in solution. This is evident for the Maillard reaction between ammonium formate and various monosaccharides for the synthesis of substituted pyrazines as well as for a Leuckart type reaction between ammonium formate and levulinic acid for the synthesis of 5-methyl-2-pyrrolidone. Furthermore, reaction of ammonium formate with citric acid for the synthesis of yet undiscovered fluorophores, shows that synthesis in REM can open up unexpected reaction pathways.
Another focus of the thesis is the study of water as a third component in the REM. As a result, the concept of two different dilution regimes (tertiary REM and in REM in solvent) appears useful for understanding the influence of water. It is shown that small amounts of water can be of great benefit for the reaction, by reducing viscosity and at the same time increasing reaction yields.
REM based on ammonium formate and organic acids are employed for lignocellulosic biomass treatment. The thesis thereby introduces an alternative approach towards lignocellulosic biomass fractionation that promises a considerable process intensification by the simultaneous generation of cellulose and lignin as well as the production of value-added chemicals from REM components. The thesis investigates the generated cellulose and the pathway to nanocellulose generation and also includes the structural analysis of extracted lignin.
Finally, the thesis investigates the potential of microwave heating to run chemical reactions in REM and describes the synergy between these two approaches. Microwave heating for chemical reactions and the use of eutectic mixtures as alternative reaction media are two research fields that are often described in the scope of green chemistry. The thesis will therefore also contain a closer inspection of this terminology and its greater goal of sustainability.
The Lyman-𝛼 (Ly𝛼) line commonly assists in the detection of high-redshift galaxies, the so-called Lyman-alpha emitters (LAEs). LAEs are useful tools to study the baryonic matter distribution of the high-redshift universe. Exploring their spatial distribution not only reveals the large-scale structure of the universe at early epochs, but it also provides an insight into the early formation and evolution of the galaxies we observe today. Because dark matter halos (DMHs) serve as sites of galaxy formation, the LAE distribution also traces that of the underlying dark matter. However, the details of this relation and their co-evolution over time remain unclear. Moreover, theoretical studies predict that the spatial distribution of LAEs also impacts their own circumgalactic medium (CGM) by influencing their extended Ly𝛼 gaseous halos (LAHs), whose origin is still under investigation. In this thesis, I make several contributions to improve the knowledge on these fields using samples of LAEs observed with the Multi Unit Spectroscopic Explorer (MUSE) at redshifts of 3 < 𝑧 < 6.
Diversity is a term that is broadly used and challenging for informatics research, development and education. Diversity concerns may relate to unequal participation, knowledge and methodology, curricula, institutional planning etc. For a lot of these areas, measures, guidelines and best practices on diversity awareness exist. A systemic, sustainable impact of diversity measures on informatics is still largely missing. In this paper I explore what working with diversity and gender concepts in informatics entails, what the main challenges are and provide thoughts for improvement. The paper includes definitions of diversity and intersectionality, reflections on the disciplinary basis of informatics and practical implications of integrating diversity in informatics research and development. In the final part, two concepts from the social sciences and the humanities, the notion of “third space”/hybridity and the notion of “feminist ethics of care”, serve as a lens to foster more sustainable ways of working with diversity in informatics.
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.
Solar photocatalysis is the one of leading concepts of research in the current paradigm of sustainable chemical industry. For actual practical implementation of sunlight-driven catalytic processes in organic synthesis, a cheap, efficient, versatile and robust heterogeneous catalyst is necessary. Carbon nitrides are a class of organic semiconductors who are known to fulfill these requirements.
First, current state of solar photocatalysis in economy, industry and lab research is overviewed, outlining EU project funding, prospective synthetic and reforming bulk processes, small scale solar organic chemistry, and existing reactor designs and prototypes, concluding feasibility of the approach.
Then, the photocatalytic aerobic cleavage of oximes to corresponding aldehydes and ketones by anionic poly(heptazine imide) carbon nitride is discussed. The reaction provides a feasible method of deprotection and formation of carbonyl compounds from nitrosation products and serves as a convenient model to study chromoselectivity and photophysics of energy transfer in heterogeneous photocatalysis.
Afterwards, the ability of mesoporous graphitic carbon nitride to conduct proton-coupled electron transfer was utilized for the direct oxygenation of 1,3-oxazolidin-2-ones to corresponding 1,3-oxazlidine-2,4-diones. This reaction provides an easier access to a key scaffold of diverse types of drugs and agrochemicals.
Finally, a series of novel carbon nitrides based on poly(triazine imide) and poly(heptazine imide) structure was synthesized from cyanamide and potassium rhodizonate. These catalysts demonstrated a good performance in a set of photocatalytic benchmark reactions, including aerobic oxidation, dual nickel photoredox catalysis, hydrogen peroxide evolution and chromoselective transformation of organosulfur precursors.
Concluding, the scope of carbon nitride utilization for net-oxidative and net-neutral photocatalytic processes was expanded, and a new tunable platform for catalyst synthesis was discovered.
While inequality of opportunity (IOp) in earnings is well studied, the literature on IOp in individual net wealth is scarce to non-existent. This is problematic because both theoretical and empirical evidence show that the position in the wealth and income distribution can significantly diverge.We measure ex-ante IOp in net wealth for Germany using data from the Socio-Economic Panel (SOEP). Ex-ante IOp is defined as the contribution of circumstances to the inequality in net wealth before effort is exerted. The SOEP allows for a direct mapping from individual circumstances to individual net wealth and for a detailed decomposition of net wealth inequality into a variety of circumstances; among them childhood background, intergenerational transfers, and regional characteristics. The ratio of inequality of opportunity to total inequality is stable from 2002 to 2019. This is in sharp contrast to labor earnings, where ex-ante IOp is declining over time. Our estimates suggest that about 62% of the inequality in net wealth is due to circumstances. The most important circumstances are intergenerational transfers, parental occupation, and the region of birth. In contrast, gender and individuals’ own education are the most important circumstances for earnings.
In the past decades, scholars and courts have paid considerable attention to the extraterritorial applicability of human rights treaties. By contrast, the extraterritorial application of constitutional rights has received comparable scholarly attention only in the United States. Specifically, there is a paucity of comparative research in this area, which contributes to the prevailing view that human rights law provides the proper framework under which domestic courts should examine extraterritoriality questions under constitutional law.
This article argues that domestic constitutional regimes and their judicial enforcers can and should provide an important counterweight to the deadlocked extraterritoriality debate at the international level. Using two case studies from Germany and the United States, it shows that domestic constitutional courts are sometimes better suited than treaty bodies to guard the normative values of human dignity and universality in an extraterritoriality context. This is most apparent in the case of Germany, which has a long tradition of integration into international multi-level governance systems and "bottom-up" resistance based on fundamental rights within such systems. Recent cases from the Federal Constitutional Court (Bundesverfassungsgericht) about the extraterritorial application of the Basic Law (Grundgesetz) to foreign intelligence gathering and climate change support this theory. However, an independent constitutional approach can also achieve some normative effects in domestic systems that are more isolated from the international human rights system. Thus, the US Supreme Court likewise used domestic constitutional doctrine to sidestep the American government's strictly territorial interpretation of the ICCPR and employ a functional approach to the extraterritorial applicability of fundamental rights in the case of detention of suspected terrorists in the Guantánamo Bay naval base.
The study of these two examples does not purport to be comprehensive or even representative of the world’s diverse array of constitutions and their relationships with international human rights law. However, the independent power of constitutional frameworks in these two disparate cases should all the more provide an impetus for increased comparative research into constitutional extraterritoriality regimes and their value for the project of human rights.
The Andean Cordillera is a mountain range located at the western South American margin and is part of the Eastern- Circum-Pacific orogenic Belt. The ~7000 km long mountain range is one of the longest on Earth and hosts the second largest orogenic plateau in the world, the Altiplano-Puna plateau. The Andes are known as a non-collisional subduction-type orogen which developed as a result of the interaction between the subducted oceanic Nazca plate and the South American continental plate. The different Andean segments exhibit along-strike variations of morphotectonic provinces characterized by different elevations, volcanic activity, deformation styles, crustal thickness, shortening magnitude and oceanic plate geometry. Most of the present-day elevation can be explained by crustal shortening in the last ~50 Ma, with the shortening magnitude decreasing from ~300 km in the central (15°S-30°S) segment to less than half that in the southern part (30°S-40°S). Several factors were proposed that might control the magnitude and acceleration of shortening of the Central Andes in the last 15 Ma. One important factor is likely the slab geometry. At 27-33°S, the slab dips horizontally at ~100 km depth due to the subduction of the buoyant Juan Fernandez Ridge, forming the Pampean flat-slab. This horizontal subduction is thought to influence the thermo-mechanical state of the Sierras Pampeanas foreland, for instance, by strengthening the lithosphere and promoting the thick-skinned propagation of deformation to the east, resulting in the uplift of the Sierras Pampeanas basement blocks. The flat-slab has migrated southwards from the Altiplano latitude at ~30 Ma to its present-day position and the processes and consequences associated to its passage on the contemporaneous acceleration of the shortening rate in Central Andes remain unclear. Although the passage of the flat-slab could offer an explanation to the acceleration of the shortening, the timing does not explain the two pulses of shortening at about 15 Ma and 4 Ma that are suggested from geological observations. I hypothesize that deformation in the Central Andes is controlled by a complex interaction between the subduction dynamics of the Nazca plate and the dynamic strengthening and weakening of the South American plate due to several upper plate processes. To test this hypothesis, a detailed investigation into the role of the flat-slab, the structural inheritance of the continental plate, and the subduction dynamics in the Andes is needed. Therefore, I have built two classes of numerical thermo-mechanical models: (i) The first class of models are a series of generic E-W-oriented high-resolution 2D subduction models thatinclude flat subduction in order to investigate the role of the subduction dynamics on the temporal variability of the shortening rate in the Central Andes at Altiplano latitudes (~21°S). The shortening rate from the models was then validated with the observed tectonic shortening rate in the Central Andes. (ii) The second class of models are a series of 3D data-driven models of the present-day Pampean flat-slab configuration and the Sierras Pampeanas (26-42°S). The models aim to investigate the relative contribution of the present-day flat subduction and inherited structures in the continental lithosphere on the strain localization. Both model classes were built using the advanced finite element geodynamic code ASPECT.
The first main finding of this work is to suggest that the temporal variability of shortening in the Central Andes is primarily controlled by the subduction dynamics of the Nazca plate while it penetrates into the mantle transition zone. These dynamics depends on the westward velocity of the South American plate that provides the main crustal shortening force to the Andes and forces the trench to retreat. When the subducting plate reaches the lower mantle, it buckles on it-self until the forced trench retreat causes the slab to steepen in the upper mantle in contrast with the classical slab-anchoring model. The steepening of the slab hinders the trench causing it to resist the advancing South American plate, resulting in the pulsatile shortening. This buckling and steepening subduction regime could have been initiated because of the overall decrease in the westwards velocity of the South American plate. In addition, the passage of the flat-slab is required to promote the shortening of the continental plate because flat subduction scrapes the mantle lithosphere, thus weakening the continental plate. This process contributes to the efficient shortening when the trench is hindered, followed by mantle lithosphere delamination at ~20 Ma. Finally, the underthrusting of the Brazilian cratonic shield beneath the orogen occurs at ~11 Ma due to the mechanical weakening of the thick sediments covered the shield margin, and due to the decreasing resistance of the weakened lithosphere of the orogen.
The second main finding of this work is to suggest that the cold flat-slab strengthens the overriding continental lithosphere and prevents strain localization. Therefore, the deformation is transmitted to the eastern front of the flat-slab segment by the shear stress operating at the subduction interface, thus the flat-slab acts like an indenter that “bulldozes” the mantle-keel of the continental lithosphere. The offset in the propagation of deformation to the east between the flat and steeper slab segments in the south causes the formation of a transpressive dextral shear zone. Here, inherited faults of past tectonic events are reactivated and further localize the deformation in an en-echelon strike-slip shear zone, through a mechanism that I refer to as “flat-slab conveyor”. Specifically, the shallowing of the flat-slab causes the lateral deformation, which explains the timing of multiple geological events preceding the arrival of the flat-slab at 33°S. These include the onset of the compression and of the transition between thin to thick-skinned deformation styles resulting from the crustal contraction of the crust in the Sierras Pampeanas some 10 and 6 Myr before the Juan Fernandez Ridge collision at that latitude, respectively.
The knowledge of transformation pathways and identification of transformation products (TPs) of veterinary drugs is important for animal health, food, and environmental matters. The active agent Monensin (MON) belongs to the ionophore antibiotics and is widely used as a veterinary drug against coccidiosis in broiler farming. However, no electrochemically (EC) generated TPs of MON have been described so far. In this study, the online coupling of EC and mass spectrometry (MS) was used for the generation of oxidative TPs. EC-conditions were optimized with respect to working electrode material, solvent, modifier, and potential polarity. Subsequent LC/HRMS (liquid+ chromatography/high resolution mass spectrometry) and MS/MS experiments were performed to identify the structures of derived TPs by a suspected target analysis. The obtained EC-results were compared to TPs observed in metabolism tests with microsomes and hydrolysis experiments of MON. Five previously undescribed TPs of MON were identified in our EC/MS based study and one TP, which was already known from literature and found by a microsomal assay, could be confirmed. Two and three further TPs were found as products in microsomal tests and following hydrolysis, respectively. We found decarboxylation, O-demethylation and acid-catalyzed ring-opening reactions to be the major mechanisms of MON transformation