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Institute
- Institut für Physik und Astronomie (28)
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Health effects, attributed to the environmental pollution resulted from using solvents such as benzene, are relatively unexplored among petroleum workers, personal use, and laboratory researchers. Solvents can cause various health problems, such as neurotoxicity, immunotoxicity, and carcinogenicity. As such it can be absorbed via epidermal or respiratory into the human body resulting in interacting with molecules that are responsible for biochemical and physiological processes of the brain.
Owing to the ever-growing demand for finding a solution, an Ionic liquid can use as an alternative solvent. Ionic liquids are salts in a liquid state at low temperature (below 100 C), or even at room temperature. Ionic liquids impart a unique architectural platform, which has been interesting because of their unusual properties that can be tuned by simple ways such as mixing two ionic liquids.
Ionic liquids not only used as reaction solvents but they became a key developing for novel applications based on their thermal stability, electric conductivity with very low vapor pressure in contrast to the conventional solvents.
In this study, ionic liquids were used as a solvent and reactant at the same time for the novel nanomaterials synthesis for different applications including solar cells, gas sensors, and water splitting.
The field of ionic liquids continues to grow, and become one of the most important branches of science. It appears to be at a point where research and industry can work together in a new way of thinking for green chemistry and sustainable production.
The climate is a complex dynamical system involving interactions and feedbacks among different processes at multiple temporal and spatial scales. Although numerous studies have attempted to understand the climate system, nonetheless, the studies investigating the multiscale characteristics of the climate are scarce. Further, the present set of techniques are limited in their ability to unravel the multi-scale variability of the climate system. It is completely plausible that extreme events and abrupt transitions, which are of great interest to climate community, are resultant of interactions among processes operating at multi-scale. For instance, storms, weather patterns, seasonal irregularities such as El Niño, floods and droughts, and decades-long climate variations can be better understood and even predicted by quantifying their multi-scale dynamics. This makes a strong argument to unravel the interaction and patterns of climatic processes at different scales. With this background, the thesis aims at developing measures to understand and quantify multi-scale interactions within the climate system.
In the first part of the thesis, I proposed two new methods, viz, multi-scale event synchronization (MSES) and wavelet multi-scale correlation (WMC) to capture the scale-specific features present in the climatic processes. The proposed methods were tested on various synthetic and real-world time series in order to check their applicability and replicability. The results indicate that both methods (WMC and MSES) are able to capture scale-specific associations that exist between processes at different time scales in a more detailed manner as compared to the traditional single scale counterparts.
In the second part of the thesis, the proposed multi-scale similarity measures were used in constructing climate networks to investigate the evolution of spatial connections within climatic processes at multiple timescales. The proposed methods WMC and MSES, together with complex network were applied to two different datasets.
In the first application, climate networks based on WMC were constructed for the univariate global sea surface temperature (SST) data to identify and visualize the SSTs patterns that develop very similarly over time and distinguish them from those that have long-range teleconnections to other ocean regions. Further investigations of climate networks on different timescales revealed (i) various high variability and co-variability regions, and (ii) short and long-range teleconnection regions with varying spatial distance. The outcomes of the study not only re-confirmed the existing knowledge on the link between SST patterns like El Niño Southern Oscillation and the Pacific Decadal Oscillation, but also suggested new insights into the characteristics and origins of long-range teleconnections.
In the second application, I used the developed non-linear MSES similarity measure to quantify the multivariate teleconnections between extreme Indian precipitation and climatic patterns with the highest relevance for Indian sub-continent. The results confirmed significant non-linear influences that were not well captured by the traditional methods. Further, there was a substantial variation in the strength and nature of teleconnection across India, and across time scales.
Overall, the results from investigations conducted in the thesis strongly highlight the need for considering the multi-scale aspects in climatic processes, and the proposed methods provide robust framework for quantifying the multi-scale characteristics.
Es gibt in Berlin eine einzigartige Vereinslandschaft im Amateur – und semiprofessionellen Fußballsport, in der einst von türkischen Migranten gegründete Vereine einen festen Platz einnehmen. Fußballsport bietet einen sozialen Raum für Jugendliche verschiedener kultureller, ethnischer und religiöser Herkunft, in dem Gruppen gebildet werden, um gegen einander zu konkurrieren. Ebenso eröffnet Fußball dem Einzelnen die Möglichkeit, die Gültigkeit und Relevanz von Vorurteilen und von gängigen Stereotypisierungen anderer Gruppen im Spielalltag einer ständigen Prüfung zu unterziehen. Fußballspieler können sich sowohl zwischen multi-kulturellen als auch mono-ethnischen Gruppenkonstellationen, in einigen Fällen auch in transnationalen Konstellationen bewegen, womit sie dabei wesentlich an der Sinngebung ihrer eigenen sozialen Zugehörigkeit mitwirken, die sich aus dem Spannungsfeld von Selbst- und Fremdwahrnehmungsmustern ergibt. In Folge dessen werden in diesem Raum Anerkennungsmechanismen konstituiert.
Die vorliegende Dissertation befasst sich mit dem alltäglichen Leben von türkisch-stämmigen, jugendlichen Amateur- und semiprofessionellen Fußballspielern (delikanli), sowie von anderen sozialen Akteuren der türkischen Fußballwelt, wie zum Beispiel „ältere“ Fußballspieler (agbi) und Fußballtrainer (hoca). Hauptanliegen der Arbeit war die Rekonstruktion kollektiver Wahrnehmungs-, Deutungs - und Handlungsmuster von Mitgliedern türkischer Fußballvereine im allgemeinen und ihrer Selbstdarstellung aber auch ihrer Wahrnehmung der „Anderen“ im besonderen. Mittels dieser Studie sollte nachvollzogen werden, ob und inwiefern sich traditionelle soziale Verhaltensmuster der gewählten Gruppe im technisch regulierten und stark Konkurrenz-orientierten Handlungsraum widerspiegeln und die reziproken Beziehungen zwischen dem „Selbst“ und den „Anderen“ regulieren. Dabei wurde die Relevanz von herkunftsbezogenen Stereotypisierungen und Vorurteilen in der kollektiven Konstitution von Selbstwahrnehmungen und Fremdverstehen im partikularen sozialen Feld (Bourdieu, 2001) des Fußballs rekonstruiert.
In dieser Arbeit wurde darüber hinaus beleuchtet, welche Rolle türkische Fußballvereine auf der einen Seite bei der Entstehung sozialer Raumzugehörigkeit zu den Stadtquartieren in Berlin einnehmen und welche Art von Mechanismen der sozialen Integration sie in diesen Vereinen herstellen. Auf der anderen Seite wurde hinterfragt, inwiefern sie zur sozialen Kohäsion zwischen diversen Kulturen beitragen. Daher wurde geprüft, ob und inwiefern die negativ konnotierte ethnozentrische Wahrnehmung von „Differenz“ (Bielefeld, 1998), die als soziales Konstrukt zwischen autochthonen und allochthonen Gruppen hergestellt wird, durch das Engagement der Vereinsakteure einen konstruktiven Wandel erfährt.
Übergeordnetes Ziel all dieser Forschungsfragen war es, ein fundiertes Verständnis über die Rolle von türkischen Fußballvereinen als soziale Mechanismen zu erlangen und deren Funktionsweise bei der Konstitution von Anpassungsstrategien in diesem sozialen Feld untersuchen. Detailliert wurde diese Rolle unter der Konzeptualisierung von sozialen Positionierungsmuster betrachtet, die als Gefüge von Deutungen des Alltäglichen verstanden werden, das individuelle und kollektive Handlungsmuster und implizit Muster des Fremdverstehens sowie des othering im Migrationskontext reguliert. Eine Rekonstruktion der sozialen Positionierungsmuster bietet eine eingehende soziologische Untersuchung dieser Teilnehmergruppe, die zudem Aufschluss über die Bedeutung und das Verständnis von ethnischer Zugehörigkeit für letztere gibt.
Neben umfangreicher Feldbeobachtung wurden in dieser qualitativen Studie mit Spielern verschiedener Vereine insgesamt zehn Gruppendiskussionen (Bohnsack, 2004) innerhalb ihrer Mannschaften zu gemeinsamen alltäglichen Erlebnissen und Erfahrungen durchgeführt, aufgezeichnet und mittels sozialwissenschaftlichem hermeneutischem Verfahren (Soeffner, 2004) interpretiert. Auch mit anderen Vereinsmitgliedern, d. h. mit Trainern bzw. hoca, Vorsitzenden, Managern und Sponsoren wurden jeweils zehn narrative und sieben biographische Einzelinterviews sowie sieben Experteninterviews durchgeführt. Deren Analyse erlaubt es, die Rolle dieser Mitglieder sowie wirkende Autoritätsmechanismen und kollektiv konstituierte Verhaltensmuster innerhalb der gesamten Vereinsgruppe zu rekonstruieren. Dabei wurde bezweckt, die Gesamtheit des sozialen Netzwerkes bzw. die Beziehungsschemata innerhalb der türkischen Fußballvereine Berlins zu verdeutlichen.
In der Arbeit werden zwei Standpunkte der theoretischen Auseinandersetzung verwendet. Auf der einen Seite wird die Lebensweltanalyse (Schütz und Luckmann, 1979, 1990) angewendet, um das soziale Erbe der in der Vergangenheit gesellschaftlich konstituierten Titulierung „Menschen mit Migrationshintergrund“ zu rekonstruieren, bzw. den Einfluss dieser sozialen Reproduktion auf die Wahrnehmungs-, Deutungs- und Handlungsmuster der Akteure zu untersuchen. Auf der anderen Seite wird die soziale Wirkung der tatsächlichen, alltäglichen Erfahrungsschemata im sozialen Feld des Fußballs auf die Selbstpositionierungen der Akteure mittels Goffmanscher Rahmenanalyse (Goffman, 1980) herausgearbeitet.
Characterization of altered inflorescence architecture in Arabidopsis thaliana BG-5 x Kro-0 hybrid
(2018)
A reciprocal cross between two A. thaliana accessions, Kro-0 (Krotzenburg, Germany) and BG-5 (Seattle, USA), displays purple rosette leaves and dwarf bushy phenotype in F1 hybrids when grown at 17 °C and a parental-like phenotype when grown at 21 °C. This F1 temperature-dependent-dwarf-bushy phenotype is characterized by reduced growth of the primary stem together with an increased number of branches. The reduced stem growth was the strongest at the first internode. In addition, we found that a temperature switch from 21 °C to 17 °C induced the phenotype only before the formation of the first internode of the stem. Similarly, the F1 dwarf-bushy phenotype could not be reversed when plants were shifted from 17 °C to 21 °C after the first internode was formed. Metabolic analysis showed that the F1 phenotype was associated with a significant upregulation of anthocyanin(s), kaempferol(s), salicylic acid, jasmonic acid and abscisic acid. As it has been previously shown that the dwarf-bushy phenotype is linked to two loci, one on chromosome 2 from Kro-0 and one on chromosome 3 from BG-5, an artificial micro-RNA approach was used to investigate the necessary genes on these intervals. From the results obtained, it was found that two genes, AT2G14120 that encodes for a DYNAMIN RELATED PROTEIN3B and AT2G14100 that encodes a member of the Cytochrome P450 family protein CYP705A13, were necessary for the appearance of the F1 phenotype on chromosome 2. It was also discovered that AT3G61035 that encodes for another cytochrome P450 family protein CYP705A13 and AT3G60840 that encodes for a MICROTUBULE-ASSOCIATED PROTEIN65-4 on chromosome 3 were both necessary for the induction of the F1 phenotype. To prove the causality of these genes, genomic constructs of the Kro-0 candidate genes on chromosome 2 were transferred to BG-5 and genomic constructs of the chromosome 3 candidate genes from BG-5 were transferred to Kro-0. The T1 lines showed that these genes are not sufficient alone to induce the phenotype. In addition to the F1 phenotype, more severe phenotypes were observed in the F2 generations that were grouped into five different phenotypic classes. Whilst seed yield was comparable between F1 hybrids and parental lines, three phenotypic classes in the F2 generation exhibited hybrid breakdown in the form of reproductive failure. This F2 hybrid breakdown was less sensitive to temperature and showed a dose-dependent effect of the loci involved in F1 phenotype. The severest class of hybrid breakdown phenotypes was observed only in the population of backcross with the parent Kro-0, which indicates a stronger contribution of the BG-5 allele when compared to the Kro-0 allele on the hybrid breakdown phenotypes. Overall, the findings of my thesis provide a further understanding of the genetic and metabolic factors underlying altered shoot architecture in hybrid dysfunction.
This text is a contribution to the research on the worldwide success of evangelical Christianity and offers a new perspective on the relationship between late modern capitalism and evangelicalism. For this purpose, the utilization of affect and emotion in evangelicalism towards the mobilization of its members will be examined in order to find out what similarities to their employment in late modern capitalism can be found. Different examples from within the evangelical spectrum will be analyzed as affective economies in order to elaborate how affective mobilization is crucial for evangelicalism’s worldwide success. Pivotal point of this text is the exploration of how evangelicalism is able to activate the voluntary commitment of its members, financiers, and missionaries. Gathered here are examples where both spheres—evangelicalism and late modern capitalism—overlap and reciprocate, followed by a theoretical exploration of how the findings presented support a view of evangelicalism as an inner-worldly narcissism that contributes to an assumed re-enchantment of the world.
The concept of hydrologic connectivity summarizes all flow processes that link separate regions of a landscape. As such, it is a central theme in the field of catchment hydrology, with influence on neighboring disciplines such as ecology and geomorphology. It is widely acknowledged to be an important key in understanding the response behavior of a catchment and has at the same time inspired research on internal processes over a broad range of scales. From this process-hydrological point of view, hydrological connectivity is the conceptual framework to link local observations across space and scales.
This is the context in which the four studies this thesis comprises of were conducted. The focus was on structures and their spatial organization as important control on preferential subsurface flow. Each experiment covered a part of the conceptualized flow path from hillslopes to the stream: soil profile, hillslope, riparian zone, and stream.
For each study site, the most characteristic structures of the investigated domain and scale, such as slope deposits and peat layers were identified based on preliminary or previous investigations or literature reviews. Additionally, further structural data was collected and topographical analyses were carried out. Flow processes were observed either based on response observations (soil moisture changes or discharge patterns) or direct measurement (advective heat transport). Based on these data, the flow-relevance of the characteristic structures was evaluated, especially with regard to hillslope to stream connectivity.
Results of the four studies revealed a clear relationship between characteristic spatial structures and the hydrological behavior of the catchment. Especially the spatial distribution of structures throughout the study domain and their interconnectedness were crucial for the establishment of preferential flow paths and their relevance for large-scale processes. Plot and hillslope-scale irrigation experiments showed that the macropores of a heterogeneous, skeletal soil enabled preferential flow paths at the scale of centimeters through the otherwise unsaturated soil. These flow paths connected throughout the soil column and across the hillslope and facilitated substantial amounts of vertical and lateral flow through periglacial slope deposits.
In the riparian zone of the same headwater catchment, the connectivity between hillslopes and stream was controlled by topography and the dualism between characteristic subsurface structures and the geomorphological heterogeneity of the stream channel. At the small scale (1 m to 10 m) highest gains always occurred at steps along the longitudinal streambed profile, which also controlled discharge patterns at the large scale (100 m) during base flow conditions (number of steps per section). During medium and high flow conditions, however, the impact of topography and parafluvial flow through riparian zone structures prevailed and dominated the large-scale response patterns.
In the streambed of a lowland river, low permeability peat layers affected the connectivity between surface water and groundwater, but also between surface water and the hyporheic zone. The crucial factor was not the permeability of the streambed itself, but rather the spatial arrangement of flow-impeding peat layers, causing increased vertical flow through narrow “windows” in contrast to predominantly lateral flow in extended areas of high hydraulic conductivity sediments.
These results show that the spatial organization of structures was an important control for hydrological processes at all scales and study areas. In a final step, the observations from different scales and catchment elements were put in relation and compared. The main focus was on the theoretical analysis of the scale hierarchies of structures and processes and the direction of causal dependencies in this context. Based on the resulting hierarchical structure, a conceptual framework was developed which is capable of representing the system’s complexity while allowing for adequate simplifications.
The resulting concept of the parabolic scale series is based on the insight that flow processes in the terrestrial part of the catchment (soil and hillslopes) converge. This means that small-scale processes assemble and form large-scale processes and responses. Processes in the riparian zone and the streambed, however, are not well represented by the idea of convergence. Here, the large-scale catchment signal arrives and is modified by structures in the riparian zone, stream morphology, and the small-scale interactions between surface water and groundwater. Flow paths diverge and processes can better be represented by proceeding from large scales to smaller ones. The catchment-scale representation of processes and structures is thus the conceptual link between terrestrial hillslope processes and processes in the riparian corridor.
Plastic pollution is ubiquitous on the planet since several millions of tons of plastic waste enter aquatic ecosystems each year. Furthermore, the amount of plastic produced is expected to increase exponentially shortly. The heterogeneity of materials, additives and physical characteristics of plastics are typical of these emerging contaminants and affect their environmental fate in marine and freshwaters. Consequently, plastics can be found in the water column, sediments or littoral habitats of all aquatic ecosystems. Most of this plastic debris will fragment as a product of physical, chemical and biological forces, producing particles of small size. These particles (< 5mm) are known as “microplastics” (MP). Given their high surface-to-volume ratio, MP stimulate biofouling and the formation of biofilms in aquatic systems.
As a result of their unique structure and composition, the microbial communities in MP biofilms are referred to as the “Plastisphere.” While there is increasing data regarding the distinctive composition and structure of the microbial communities that form part of the plastisphere, scarce information exists regarding the activity of microorganisms in MP biofilms. This surface-attached lifestyle is often associated with the increase in horizontal gene transfer (HGT) among bacteria. Therefore, this type of microbial activity represents a relevant function worth to be analyzed in MP biofilms. The horizontal exchange of mobile genetic elements (MGEs) is an essential feature of bacteria. It accounts for the rapid evolution of these prokaryotes and their adaptation to a wide variety of environments. The process of HGT is also crucial for spreading antibiotic resistance and for the evolution of pathogens, as many MGEs are known to contain antibiotic resistance genes (ARGs) and genetic determinants of pathogenicity.
In general, the research presented in this Ph.D. thesis focuses on the analysis of HGT and heterotrophic activity in MP biofilms in aquatic ecosystems. The primary objective was to analyze the potential of gene exchange between MP bacterial communities vs. that of the surrounding water, including bacteria from natural aggregates. Moreover, the thesis addressed the potential of MP biofilms for the proliferation of biohazardous bacteria and MGEs from wastewater treatment plants (WWTPs) and associated with antibiotic resistance. Finally, it seeks to prove if the physiological profile of MP biofilms under different limnological conditions is divergent from that of the water communities. Accordingly, the thesis is composed of three independent studies published in peer-reviewed journals. The two laboratory studies were performed using both model and environmental microbial communities. In the field experiment, natural communities from freshwater ecosystems were examined.
In Chapter I, the inflow of treated wastewater into a temperate lake was simulated with a concentration gradient of MP particles. The effects of MP on the microbial community structure and the occurrence of integrase 1 (int 1) were followed. The int 1 is a marker associated with mobile genetic elements and known as a proxy for anthropogenic effects on the spread of antimicrobial resistance genes. During the experiment, the abundance of int1 increased in the plastisphere with increasing MP particle concentration, but not in the surrounding water. In addition, the microbial community on MP was more similar to the original wastewater community with increasing microplastic concentrations. Our results show that microplastic particles indeed promote persistence of standard indicators of microbial anthropogenic pollution in natural waters.
In Chapter II, the experiments aimed to compare the permissiveness of aquatic bacteria towards model antibiotic resistance plasmid pKJK5, between communities that form biofilms on MP vs. those that are free-living. The frequency of plasmid transfer in bacteria associated with MP was higher when compared to bacteria that are free-living or in natural aggregates. Moreover, comparison increased gene exchange occurred in a broad range of phylogenetically-diverse bacteria. The results indicate a different activity of HGT in MP biofilms, which could affect the ecology of aquatic microbial communities on a global scale and the spread of antibiotic resistance.
Finally, in Chapter III, physiological measurements were performed to assess whether microorganisms on MP had a different functional diversity from those in water. General heterotrophic activity such as oxygen consumption was compared in microcosm assays with and without MP, while diversity and richness of heterotrophic activities were calculated by using Biolog® EcoPlates. Three lakes with different nutrient statuses presented differences in MP-associated biomass build up. Functional diversity profiles of MP biofilms in all lakes differed from those of the communities in the surrounding water, but only in the oligo-mesotrophic lake MP biofilms had a higher functional richness compared to the ambient water. The results support that MP surfaces act as new niches for aquatic microorganisms and can affect global carbon dynamics of pelagic environments.
Overall, the experimental works presented in Chapters I and II support a scenario where MP pollution affects HGT dynamics among aquatic bacteria. Among the consequences of this alteration is an increase in the mobilization and transfer efficiency of ARGs. Moreover, it supposes that changes in HGT can affect the evolution of bacteria and the processing of organic matter, leading to different catabolic profiles such as demonstrated in Chapter III. The results are discussed in the context of the fate and magnitude of plastic pollution and the importance of HGT for bacterial evolution and the microbial loop, i.e., at the base of aquatic food webs. The thesis supports a relevant role of MP biofilm communities for the changes observed in the aquatic microbiome as a product of intense human intervention.
Future magnetic recording industry needs a high-density data storage technology. However, switching the magnetization of small bits requires high magnetic fields that cause excessive heat dissipation. Therefore, controlling magnetism without applying external magnetic field is an important research topic for potential applications in data storage devices with low power consumption. Among the different approaches being investigated, two of them stand out, namely i) all-optical helicity dependent switching (AO-HDS) and ii) ferroelectric control of magnetism. This thesis aims to contribute towards a better understanding of the physical processes behinds these effects as well as reporting new and exciting possibility for the optical and/or electric control of magnetic properties. Hence, the thesis contains two differentiated chapters of results; the first devoted to AO-HDS on TbFe alloys and the second to the electric field control of magnetism in an archetypal Fe/BaTiO3 system.
In the first part, the scalability of the AO-HDS to small laser spot-sizes of few microns in the ferrimagnetic TbFe alloy is investigated by spatially resolving the magnetic contrast with photo-emission electron microscopy (PEEM) and X-ray magnetic circular dichroism (XMCD). The results show that the AO-HDS is a local effect within the laser spot size that occurs in the ring-shaped region in the vicinity of thermal demagnetization. Within the ring region, the helicity dependent switching occurs via thermally activated domain wall motion. Further, the thesis reports on a novel effect of thickness dependent inversion of the switching orientation. It addresses some of the important questions like the role of laser heating and the microscopic mechanism driving AO-HDS.
The second part of the thesis focuses on the electric field control of magnetism in an artificial multiferroic heterostructure. The sample consists of an Fe wedge with thickness varying between 0:5 nm and 3 nm, deposited on top of a ferroelectric and ferroelastic BaTiO3 [001]-oriented single crystal substrate. Here, the magnetic contrast is imaged via PEEM and XMCD as a function of out-of-plane voltage. The results show the evidence of the electric field control of superparamagnetism mediated by a ferroelastic modification of the magnetic anisotropy. The changes in the magnetoelastic anisotropy drive the transition from the superparamagnetic to superferromagnetic state at localized sample positions.
Business process management is an acknowledged asset for running an organization in a productive and sustainable way. One of the most important aspects of business process management, occurring on a daily basis at all levels, is decision making. In recent years, a number of decision management frameworks have appeared in addition to existing business process management systems. More recently, Decision Model and Notation (DMN) was developed by the OMG consortium with the aim of complementing the widely used Business Process Model and Notation (BPMN). One of the reasons for the emergence of DMN is the increasing interest in the evolving paradigm known as the separation of concerns. This paradigm states that modeling decisions complementary to processes reduces process complexity by externalizing decision logic from process models and importing it into a dedicated decision model. Such an approach increases the agility of model design and execution. This provides organizations with the flexibility to adapt to the ever increasing rapid and dynamic changes in the business ecosystem. The research gap, identified by us, is that the separation of concerns, recommended by DMN, prescribes the externalization of the decision logic of process models in one or more separate decision models, but it does not specify this can be achieved.
The goal of this thesis is to overcome the presented gap by developing a framework for discovering decision models in a semi-automated way from information about existing process decision making. Thus, in this thesis we develop methodologies to extract decision models from: (1) control flow and data of process models that exist in enterprises; and (2) from event logs recorded by enterprise information systems, encapsulating day-to-day operations. Furthermore, we provide an extension of the methodologies to discover decision models from event logs enriched with fuzziness, a tool dealing with partial knowledge of the process execution information. All the proposed techniques are implemented and evaluated in case studies using real-life and synthetic process models and event logs. The evaluation of these case studies shows that the proposed methodologies provide valid and accurate output decision models that can serve as blueprints for executing decisions complementary to process models. Thus, these methodologies have applicability in the real world and they can be used, for example, for compliance checks, among other uses, which could improve the organization's decision making and hence it's overall performance.
New bio-based polymers
(2018)
Redox-responsive polymers, such as poly(disulfide)s, are a versatile class of polymers with potential applications including gene- and drug-carrier systems. Their degradability under reductive conditions allows for a controlled response to the different redox states that are present throughout the body. Poly(disulfide)s are typically synthesized by step growth polymerizations. Step growth polymerizations, however, may suffer from low conversions and therefore low molar masses, limiting potential applications. The purpose of this thesis was therefore to find and investigate new synthetic routes towards the synthesis of amino acid-based poly(disulfide)s.
The different routes in this thesis include entropy-driven ring opening polymerizations of novel macrocyclic monomers, derived from cystine derivatives. These monomers were obtained with overall yields of up to 77% and were analyzed by mass spectrometry as well as by 1D and 2D NMR spectroscopy. The kinetics of the entropy-driven ring-opening metathesis polymerization (ED-ROMP) were thoroughly investigated in dependence of temperature, monomer concentration, and catalyst concentration. The polymerization was optimized to yield poly(disulfide)s with weight average molar masses of up to 80 kDa and conversions of ~80%, at the thermodynamic equilibrium. Additionally, an alternative metal free polymerization, namely the entropy-driven ring-opening disulfide metathesis polymerization (ED-RODiMP) was established for the polymerization of the macrocyclic monomers. The effect of different solvents, concentrations and catalyst loadings on the polymerization process and its kinetics were studied. Polymers with very high weight average molar masses of up to 177 kDa were obtained. Moreover, various post-polymerization reactions were successfully performed.
This work provides the first example of the homopolymerization of endo-cyclic disulfides by ED-ROMP and the first substantial study into the kinetics of the ED-RODiMP process.
Causes for slow weathering and erosion in the steep, warm, monsoon-subjected Highlands of Sri Lanka
(2018)
In the Highlands of Sri Lanka, erosion and chemical weathering rates are among the lowest for global mountain denudation. In this tropical humid setting, highly weathered deep saprolite profiles have developed from high-grade metamorphic charnockite during spheroidal weathering of the bedrock. The spheroidal weathering produces rounded corestones and spalled rindlets at the rock-saprolite interface. I used detailed textural, mineralogical, chemical, and electron-microscopic (SEM, FIB, TEM) analyses to identify the factors limiting the rate of weathering front advance in the profile, the sequence of weathering reactions, and the underlying mechanisms. The first mineral attacked by weathering was found to be pyroxene initiated by in situ Fe oxidation, followed by in situ biotite oxidation. Bulk dissolution of the primary minerals is best described with a dissolution – re-precipitation process, as no chemical gradients towards the mineral surface and sharp structural boundaries are observed at the nm scale. Only the local oxidation in pyroxene and biotite is better described with an ion by ion process. The first secondary phases are oxides and amorphous precipitates from which secondary minerals (mainly smectite and kaolinite) form. Only for biotite direct solid state transformation to kaolinite is likely. The initial oxidation of pyroxene and biotite takes place in locally restricted areas and is relatively fast: log J = -11 molmin/(m2 s). However, calculated corestone-scale mineral oxidation rates are comparable to corestone-scale mineral dissolution rates: log R = -13 molpx/(m2 s) and log R = -15 molbt/(m2 s). The oxidation reaction results in a volume increase. Volumetric calculations suggest that this observed oxidation leads to the generation of porosity due to the formation of micro-fractures in the minerals and the bedrock allowing for fluid transport and subsequent dissolution of plagioclase. At the scale of the corestone, this fracture reaction is responsible for the larger fractures that lead to spheroidal weathering and to the formation of rindlets. Since these fractures have their origin from the initial oxidational induced volume increase, oxidation is the rate limiting parameter for weathering to take place. The ensuing plagioclase weathering leads to formation of high secondary porosity in the corestone over a distance of only a few cm and eventually to the final disaggregation of bedrock to saprolite. As oxidation is the first weathering reaction, the supply of O2 is a rate-limiting factor for chemical weathering. Hence, the supply of O2 and its consumption at depth connects processes at the weathering front with erosion at the surface in a feedback mechanism. The strength of the feedback depends on the relative weight of advective versus diffusive transport of O2 through the weathering profile. The feedback will be stronger with dominating diffusive transport. The low weathering rate ultimately depends on the transport of O2 through the whole regolith, and on lithological factors such as low bedrock porosity and the amount of Fe-bearing primary minerals. In this regard the low-porosity charnockite with its low content of Fe(II) bearing minerals impedes fast weathering reactions. Fresh weatherable surfaces are a pre-requisite for chemical weathering. However, in the case of the charnockite found in the Sri Lankan Highlands, the only process that generates these surfaces is the fracturing induced by oxidation. Tectonic quiescence in this region and low pre-anthropogenic erosion rate (attributed to a dense vegetation cover) minimize the rejuvenation of the thick and cohesive regolith column, and lowers weathering through the feedback with erosion.
For more than two centuries, plant ecologists have aimed to understand how environmental gradients and biotic interactions shape the distribution and co-occurrence of plant species. In recent years, functional trait–based approaches have been increasingly used to predict patterns of species co-occurrence and species distributions along environmental gradients (trait–environment relationships). Functional traits are measurable properties at the individual level that correlate well with important processes. Thus, they allow us to identify general patterns by synthesizing studies across specific taxonomic compositions, thereby fostering our understanding of the underlying processes of species assembly. However, the importance of specific processes have been shown to be highly dependent on the spatial scale under consideration. In particular, it remains uncertain which mechanisms drive species assembly and allow for plant species coexistence at smaller, more local spatial scales. Furthermore, there is still no consensus on how particular environmental gradients affect the trait composition of plant communities. For example, increasing drought because of climate change is predicted to be a main threat to plant diversity, although it remains unclear which traits of species respond to increasing aridity. Similarly, there is conflicting evidence of how soil fertilization affects the traits related to establishment ability (e.g., seed mass). In this cumulative dissertation, I present three empirical trait-based studies that investigate specific research questions in order to improve our understanding of species distributions along environmental gradients.
In the first case study, I analyze how annual species assemble at the local scale and how environmental heterogeneity affects different facets of biodiversity—i.e. taxonomic, functional, and phylogenetic diversity—at different spatial scales. The study was conducted in a semi-arid environment at the transition zone between desert and Mediterranean ecosystems that features a sharp precipitation gradient (Israel). Different null model analyses revealed strong support for environmentally driven species assembly at the local scale, since species with similar traits tended to co-occur and shared high abundances within microsites (trait convergence). A phylogenetic approach, which assumes that closely related species are functionally more similar to each other than distantly related ones, partly supported these results. However, I observed that species abundances within microsites were, surprisingly, more evenly distributed across the phylogenetic tree than expected (phylogenetic overdispersion). Furthermore, I showed that environmental heterogeneity has a positive effect on diversity, which was higher on functional than on taxonomic diversity and increased with spatial scale. The results of this case study indicate that environmental heterogeneity may act as a stabilizing factor to maintain species diversity at local scales, since it influenced species distribution according to their traits and positively influenced diversity. All results were constant along the precipitation gradient.
In the second case study (same study system as case study one), I explore the trait responses of two Mediterranean annuals (Geropogon hybridus and Crupina crupinastrum) along a precipitation gradient that is comparable to the maximum changes in precipitation predicted to occur by the end of this century (i.e., −30%). The heterocarpic G. hybridus showed strong trends in seed traits, suggesting that dispersal ability increased with aridity. By contrast, the homocarpic C. crupinastrum showed only a decrease in plant height as aridity increased, while leaf traits of both species showed no consistent pattern along the precipitation gradient. Furthermore, variance decomposition of traits revealed that most of the trait variation observed in the study system was actually found within populations. I conclude that trait responses towards aridity are highly species-specific and that the amount of precipitation is not the most striking environmental factor at this particular scale.
In the third case study, I assess how soil fertilization mediates—directly by increased nutrient addition and indirectly by increased competition—the effect of seed mass on establishment ability. For this experiment, I used 22 species differing in seed mass from dry grasslands in northeastern Germany and analyzed the interacting effects of seed mass with nutrient availability and competition on four key components of seedling establishment: seedling emergence, time of seedling emergence, seedling survival, and seedling growth. (Time of) seedling emergence was not affected by seed mass. However, I observed that the positive effect of seed mass on seedling survival is lowered under conditions of high nutrient availability, whereas the positive effect of seed mass on seedling growth was only reduced by competition. Based on these findings, I developed a conceptual model of how seed mass should change along a soil fertility gradient in order to reconcile conflicting findings from the literature. In this model, seed mass shows a U-shaped pattern along the soil fertility gradient as a result of changing nutrient availability and competition.
Overall, the three case studies highlight the role of environmental factors on species distribution and co-occurrence. Moreover, the findings of this thesis indicate that spatial heterogeneity at local scales may act as a stabilizing factor that allows species with different traits to coexist. In the concluding discussion, I critically debate intraspecific trait variability in plant community ecology, the use of phylogenetic relationships and easily measured key functional traits as a proxy for species’ niches. Finally, I offer my outlook for the future of functional plant community research.
Biological invasions are the dispersal and following establishment of species outside their native habitat. Due to globalisation, connectivity of regions and climate changes the number of invasive species and their successful establishment is rising. The impact of these species is mostly negative, can induce community and habitat alterations, and is one main cause for biodiversity loss. This impact is particularly high and less researched in aquatic systems and microbial organisms and despite the high impact, the knowledge about overall mechanisms and specific factors affecting invasions are not fully understood. In general, the characteristics of the habitat, native community and invader determine the invasiveness.
In this thesis, I aimed to provide a better understanding of aquatic invasions focusing on the invader and its traits and identity. This thesis used a set of 12 strains of the invasive cyanobacterium <i>Cylindrospermopsis raciborskii</i> to examine the effect and impact of the invaders’ identity and genetic diversity. Further, the effect of timing on the invasion potential and success was determined, because aquatic systems in particular undergo seasonal fluctuations.
Most studies revealed a higher invasion success with increasing genetic diversity. Here, the increase of the genetic diversity, by either strain richness or phylogenetic dissimilarity, is not firstly driving the invasion, but the strain-identity. The high variability among the strains in traits important for invasions led to the highly varying strain-specific invasion success. This success was most dependent on nitrogen uptake and efficient resource use. The lower invasion success into communities comprising further N-fixing species indicates <i>C. raciborskii</i> can use this advantage only without the presence of competitive species. The relief of grazing pressure, which is suggested to be more important in aquatic invasions, was only promoting the invasion when unselective and larger consumers were present. High abundances of unselective consumers hampered the invasion success.
This indicates a more complex and temporal interplay of competitive and consumptive resistance mechanisms during the invasion process. Further, the fluctuation abundance and presence of competitors (= primary producers) and consumers (= zooplankton) in lakes can open certain ‘invasion windows’.
Remarkably, the composition of the resident community was also strain-specific affected and altered, independent of a high or low invasion success. Prior, this was only documented on the species level. Further, investigations on the population of invasive strains can reveal more about the invasion patterns and how multiple strain invasions change resident communities.
The present dissertation emphasises the importance of invader-addition experiments with a community context and the importance of the strain-level for microbial invasions and in general, e.g. for community assemblies and the outcome of experiments. The strain-specific community changes, also after days, may explain some sudden changes in communities, which have not been explained yet. This and further knowledge may also facilitate earlier and less cost-intensive management to step in, because these species are rarely tracked until they reach a high abundance or bloom, because of their small size.
Concluded for <i>C. raciborskii</i>, it shows that this species is no ‘generalistic’ invader and its invasion success depends more on the competitor presence than grazing pressure. This may explain its, still unknown, invasion pattern, as <i>C. raciborskii</i> is not found in all lakes of a region.
Spatio-temporal data denotes a category of data that contains spatial as well as temporal components. For example, time-series of geo-data, thematic maps that change over time, or tracking data of moving entities can be interpreted as spatio-temporal data.
In today's automated world, an increasing number of data sources exist, which constantly generate spatio-temporal data. This includes for example traffic surveillance systems, which gather movement data about human or vehicle movements, remote-sensing systems, which frequently scan our surroundings and produce digital representations of cities and landscapes, as well as sensor networks in different domains, such as logistics, animal behavior study, or climate research.
For the analysis of spatio-temporal data, in addition to automatic statistical and data mining methods, exploratory analysis methods are employed, which are based on interactive visualization. These analysis methods let users explore a data set by interactively manipulating a visualization, thereby employing the human cognitive system and knowledge of the users to find patterns and gain insight into the data.
This thesis describes a software framework for the visualization of spatio-temporal data, which consists of GPU-based techniques to enable the interactive visualization and exploration of large spatio-temporal data sets. The developed techniques include data management, processing, and rendering, facilitating real-time processing and visualization of large geo-temporal data sets. It includes three main contributions:
- Concept and Implementation of a GPU-Based Visualization Pipeline.
The developed visualization methods are based on the concept of a GPU-based visualization pipeline, in which all steps -- processing, mapping, and rendering -- are implemented on the GPU. With this concept, spatio-temporal data is represented directly in GPU memory, using shader programs to process and filter the data, apply mappings to visual properties, and finally generate the geometric representations for a visualization during the rendering process. Data processing, filtering, and mapping are thereby executed in real-time, enabling dynamic control over the mapping and a visualization process which can be controlled interactively by a user.
- Attributed 3D Trajectory Visualization.
A visualization method has been developed for the interactive exploration of large numbers of 3D movement trajectories. The trajectories are visualized in a virtual geographic environment, supporting basic geometries such as lines, ribbons, spheres, or tubes. Interactive mapping can be applied to visualize the values of per-node or per-trajectory attributes, supporting shape, height, size, color, texturing, and animation as visual properties. Using the dynamic mapping system, several kind of visualization methods have been implemented, such as focus+context visualization of trajectories using interactive density maps, and space-time cube visualization to focus on the temporal aspects of individual movements.
- Geographic Network Visualization.
A method for the interactive exploration of geo-referenced networks has been developed, which enables the visualization of large numbers of nodes and edges in a geographic context. Several geographic environments are supported, such as a 3D globe, as well as 2D maps using different map projections, to enable the analysis of networks in different contexts and scales. Interactive filtering, mapping, and selection can be applied to analyze these geographic networks, and visualization methods for specific types of networks, such as coupled 3D networks or temporal networks have been implemented.
As a demonstration of the developed visualization concepts, interactive visualization tools for two distinct use cases have been developed. The first contains the visualization of attributed 3D movement trajectories of airplanes around an airport. It allows users to explore and analyze the trajectories of approaching and departing aircrafts, which have been recorded over the period of a month. By applying the interactive visualization methods for trajectory visualization and interactive density maps, analysts can derive insight from the data, such as common flight paths, regular and irregular patterns, or uncommon incidents such as missed approaches on the airport.
The second use case involves the visualization of climate networks, which are geographic networks in the climate research domain. They represent the dynamics of the climate system using a network structure that expresses statistical interrelationships between different regions. The interactive tool allows climate analysts to explore these large networks, analyzing the network's structure and relating it to the geographic background. Interactive filtering and selection enables them to find patterns in the climate data and identify e.g. clusters in the networks or flow patterns.
The utilization of lignin as renewable electrode material for electrochemical energy storage is a sustainable approach for future batteries and supercapacitors. The composite electrode was fabricated from Kraft lignin and conductive carbon and the charge storage contribution was determined in terms of electrical double layer (EDL) and redox reactions. The important factors at play for achieving high faradaic charge storage capacity contribute to high surface area, accessibility of redox sites in lignin and their interaction with conductive additives. A thinner layer of lignin covering the high surface area of carbon facilitates the electron transfer process with a shorter pathway from the active sites of nonconductive lignin to the current collector leading to the improvement of faradaic charge storage capacity.
Composite electrodes from lignin and carbon would be even more sustainable if the fluorinated binder can be omitted. A new route to fabricate a binder-free composite electrode from Kraft lignin and high surface area carbon has been proposed by crosslinking lignin with glyoxal. A high molecular weight of lignin is obtained to enhance both electroactivity and binder capability in composite electrodes. The order of the processing step of crosslinking lignin on the composite electrode plays a crucial role in achieving a stable electrode and high charge storage capacity. The crosslinked lignin based electrodes are promising since they allow for more stable, sustainable, halogen-free and environmentally benign devices for energy storage applications. Furthermore, improvement of the amount of redox active groups (quinone groups) in lignin is useful to enhance the capacity in lithium battery applications. Direct oxidative demethylation by cerium ammonium nitrate has been carried out under mild conditions. This proves that an increase of quinone groups is able to enhance the performance of lithium battery. Thus, lignin is a promising material and could be a good candidate for application in sustainable energy storage devices.
Nanoparticles (NPs) are particles between 1 and 100 nanometers in size. They have attracted enormous research interests owing to their remarkable physicochemical properties and potential applications in the optics, catalysis, sensing, electronics, or optical devices. The thesis investigates systems of NPs attached to planar substrates.
In the first part of the results section of the thesis a new method is presented to immobilize NPs. In many NP applications a strong, persistent adhesion to substrates is a key requirement. Up to now this has been achieved with various methods, which are not always the optimum regarding adhesion strength or applicability. We propose a new method which uses capillarity to enhance the binding agents in the contact area between NP and substrate. The adhesion strength resulting from the new approach is investigated in detail and it is shown that the new approach is superior to older methods in several ways.
The following section presents the optical visualization of nano-sized objects through a combination of thin film surface distortion and interference enhanced optical reflection microscopy. It is a new, fast and non-destructive technique. It not only reveals the location of NPs as small as 20nm attached to planar surfaces and embedded in a molecularly thin liquid film. It also allows the measurement of the geometry of the surface distortion of the liquid film. Even for small NPs the meniscus reaches out for micrometers, which is the reason why the NPs produce such a pronounced optical footprint.
The nucleation and growth of individual bubbles is presented in chapter 5. Nucleation is a ubiquitous natural phenomenon and of great importance in numerous industrial processes. Typically it occurs on very small scales (nanometers) and it is of a random nature (thermodynamics of small systems). Up to now most experimental nucleation studies deal with a large number of individual nucleation processes to cope with its inherently statistical, spatio-temporal character. In contrast, in this thesis the individual O2-bubble formation from single localized platinum NP active site is studied experimentally. The bubble formation is initiated by the catalytic reaction of H2O2 on the Pt surface. It is studied how the bubble nucleation and growth depends on the NP size, the H2O2 concentration and the substrate surface properties. It is observed that in some cases the bubbles move laterally over the substrate surface, driven by the O2-production and the film ablation.