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Institute
- Institut für Physik und Astronomie (28)
- Institut für Biochemie und Biologie (27)
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- Potsdam Institute for Climate Impact Research (PIK) e. V. (3)
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- Institut für Mathematik (2)
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- Potsdam Research Institute for Multilingualism (PRIM) (1)
Active and passive source data from two seismic experiments within the interdisciplinary project TIPTEQ (from The Incoming Plate to mega Thrust EarthQuake processes) were used to image and identify the structural and petrophysical properties (such as P- and S-velocities, Poisson's ratios, pore pressure, density and amount of fluids) within the Chilean seismogenic coupling zone at 38.25°S, where in 1960 the largest earthquake ever recorded (Mw 9.5) occurred. Two S-wave velocity models calculated using traveltime and noise tomography techniques were merged with an existing velocity model to obtain a 2D S-wave velocity model, which gathered the advantages of each individual model. In a following step, P- and S-reflectivity images of the subduction zone were obtained using different pre stack and post-stack depth migration techniques. Among them, the recent prestack line-drawing depth migration scheme yielded revealing results. Next, synthetic seismograms modelled using the reflectivity method allowed, through their input 1D synthetic P- and S-velocities, to infer the composition and rocks within the subduction zone. Finally, an image of the subduction zone is given, jointly interpreting the results from this work with results from other studies. The Chilean seismogenic coupling zone at 38.25°S shows a continental crust with highly reflective horizontal, as well as (steep) dipping events. Among them, the Lanalhue Fault Zone (LFZ), which is interpreted to be east-dipping, is imaged to very shallow depths. Some steep reflectors are observed for the first time, for example one near the coast, related to high seismicity and another one near the LFZ. Steep shallow reflectivity towards the volcanic arc could be related to a steep west-dipping reflector interpreted as fluids and/or melts, migrating upwards due to material recycling in the continental mantle wedge. The high resolution of the S-velocity model in the first kilometres allowed to identify several sedimentary basins, characterized by very low P- and S-velocities, high Poisson's ratios and possible steep reflectivity. Such high Poisson's ratios are also observed within the oceanic crust, which reaches the seismogenic zone hydrated due to bending-related faulting. It is interpreted to release water until reaching the coast and under the continental mantle wedge. In terms of seismic velocities, the inferred composition and rocks in the continental crust is in agreement with field geology observations at the surface along the proflle. Furthermore, there is no requirement to call on the existence of measurable amounts of present-day fluids above the plate interface in the continental crust of the Coastal Cordillera and the Central Valley in this part of the Chilean convergent margin. A large-scale anisotropy in the continental crust and upper mantle, previously proposed from magnetotelluric studies, is proposed from seismic velocities. However, quantitative studies on this topic in the continental crust of the Chilean seismogenic zone at 38.25°S do not exist to date.
Earth's climate varies continuously across space and time, but humankind has witnessed only a small snapshot of its entire history, and instrumentally documented it for a mere 200 years. Our knowledge of past climate changes is therefore almost exclusively based on indirect proxy data, i.e. on indicators which are sensitive to changes in climatic variables and stored in environmental archives. Extracting the data from these archives allows retrieval of the information from earlier times. Obtaining accurate proxy information is a key means to test model predictions of the past climate, and only after such validation can the models be used to reliably forecast future changes in our warming world. The polar ice sheets of Greenland and Antarctica are one major climate archive, which record information about local air temperatures by means of the isotopic composition of the water molecules embedded in the ice. However, this temperature proxy is, as any indirect climate data, not a perfect recorder of past climatic variations. Apart from local air temperatures, a multitude of other processes affect the mean and variability of the isotopic data, which hinders their direct interpretation in terms of climate variations. This applies especially to regions with little annual accumulation of snow, such as the Antarctic Plateau. While these areas in principle allow for the extraction of isotope records reaching far back in time, a strong corruption of the temperature signal originally encoded in the isotopic data of the snow is expected. This dissertation uses observational isotope data from Antarctica, focussing especially on the East Antarctic low-accumulation area around the Kohnen Station ice-core drilling site, together with statistical and physical methods, to improve our understanding of the spatial and temporal isotope variability across different scales, and thus to enhance the applicability of the proxy for estimating past temperature variability. The presented results lead to a quantitative explanation of the local-scale (1–500 m) spatial variability in the form of a statistical noise model, and reveal the main source of the temporal variability to be the mixture of a climatic seasonal cycle in temperature and the effect of diffusional smoothing acting on temporally uncorrelated noise. These findings put significant limits on the representativity of single isotope records in terms of local air temperature, and impact the interpretation of apparent cyclicalities in the records. Furthermore, to extend the analyses to larger scales, the timescale-dependency of observed Holocene isotope variability is studied. This offers a deeper understanding of the nature of the variations, and is crucial for unravelling the embedded true temperature variability over a wide range of timescales.
Microswimmers, i.e. swimmers of micron size experiencing low Reynolds numbers, have received a great deal of attention in the last years, since many applications are envisioned in medicine and bioremediation. A promising field is the one of magnetic swimmers, since magnetism is biocom-patible and could be used to direct or actuate the swimmers. This thesis studies two examples of magnetic microswimmers from a physics point of view.
The first system to be studied are magnetic cells, which can be magnetic biohybrids (a swimming cell coupled with a magnetic synthetic component) or magnetotactic bacteria (naturally occurring bacteria that produce an intracellular chain of magnetic crystals). A magnetic cell can passively interact with external magnetic fields, which can be used for direction. The aim of the thesis is to understand how magnetic cells couple this magnetic interaction to their swimming strategies, mainly how they combine it with chemotaxis (the ability to sense external gradient of chemical species and to bias their walk on these gradients). In particular, one open question addresses the advantage given by these magnetic interactions for the magnetotactic bacteria in a natural environment, such as porous sediments. In the thesis, a modified Active Brownian Particle model is used to perform simulations and to reproduce experimental data for different systems such as bacteria swimming in the bulk, in a capillary or in confined geometries. I will show that magnetic fields speed up chemotaxis under special conditions, depending on parameters such as their swimming strategy (run-and-tumble or run-and-reverse), aerotactic strategy (axial or polar), and magnetic fields (intensities and orientations), but it can also hinder bacterial chemotaxis depending on the system.
The second example of magnetic microswimmer are rigid magnetic propellers such as helices or random-shaped propellers. These propellers are actuated and directed by an external rotating magnetic field. One open question is how shape and magnetic properties influence the propeller behavior; the goal of this research field is to design the best propeller for a given situation. The aim of the thesis is to propose a simulation method to reproduce the behavior of experimentally-realized propellers and to determine their magnetic properties. The hydrodynamic simulations are based on the use of the mobility matrix. As main result, I propose a method to match the experimental data, while showing that not only shape but also the magnetic properties influence the propellers swimming characteristics.
This project was focused on exploring the phase behavior of poly(styrene)187000-block-poly(2-vinylpyridine)203000 (SV390) with high molecular weight (390 kg/mol) in thin films, in which the self-assembly of block copolymers (BCPs) was realized via thermo-solvent annealing. The advanced processing technique of solvent vapor treatment provides controlled and stable conditions.
In Chapter 3, the factors to influence the annealing process and the swelling behavior of homopolymers are presented and discussed. The swelling behavior of BCP in films is controlled by the temperature of the vapor and of the substrate, on one hand, and variation of the saturation of the solvent vapor atmosphere (different solvents), on the other hand. Additional factors like the geometry and material of the chamber, the type of flow inside the chamber etc. also influence the reproducibility and stability of the processing. The slightly selective solvent vapor of chloroform gives 10% more swelling of P2VP than PS in films with thickness of ~40 nm.
The tunable morphology in ultrathin films of high molecular weight BCP (SV390) was investigated in Chapter 4. First, the swelling behavior can be precisely tuned by temperature and/or vapor flow separately, which provided information for exploring the multiple-parameter-influenced segmental chain mobility of polymer films. The equilibrium state of SV390 in thin films influenced by temperature was realized at various temperatures with the same degree of swelling. Various methods including characterization with SFM, metallization and RIE were used to identify the morphology of films as porous half-layer with PS dots and P2VP matrix. The kinetic investigations demonstrate that on substrates with either weak or strong interaction the original morphology of the BCP with high molecular weight is changed very fast within 5 min, and the further annealing serves for annihilation of defects.
The morphological development of symmetric BCP in films with thickness increasing from half-layer to one-layer influenced by confinement factors of gradient film thicknesses and various surface properties of substrates was studied in Chapter 5. SV390 and SV99 films show bulk lamella-forming morphology after slightly selective solvent vapor (chloroform) treatment. SV99 films show cylinder-forming morphology under strongly selective solvent vapor (toluene) treatment since the asymmetric structure (caused by toluene uptake in PS blocks only) of SV99 block copolymer during annealing. Both kinds of morphology (lamella and cylinder) are influenced by the film thickness. The annealed morphology of SV390 and SV99 influenced by the combination of confined film and substrate property is similar to the morphology on flat silicon wafers. In this chapter the gradients in the film thickness and surface properties of the substrates with regard to their influence on the morphological development in thin BCP films are presented. Directed self-assembly (graphoepitaxy) of this SV390 was also investigated to compare with systematically reported SV99.
In Chapter 6 an approach to induced oriented microphase separation in thick block copolymer films via treatment with the oriented vapor flow using mini-extruder is envisaged to be an alternative to existing methodologies, e.g. via non-solvent-induced phase separation. The preliminary tests performed in this study confirm potential perspective of this method, which alters the structure through the bulk of the film (as revealed by SAXS measurements), but more detailed studies have to be conducted in order to optimize the preparation.
East Africa is a natural laboratory: Studying its unique geological and biological history can help us better inform our theories and models. Studying its present and future can help us protect its globally important biodiversity and ecosystem services. East African vegetation plays a central role in all these aspects, and this dissertation aims to quantify its dynamics through computer simulations.
Computer models help us recreate past settings, forecast into the future or conduct simulation experiments that we cannot otherwise perform in the field. But before all that, one needs to test their performance. The outputs that the model produced using the present day-inputs, agreed well with present-day observations of East African vegetation. Next, I simulated past vegetation for which we have fossil pollen data to compare. With computer models, we can fill the gaps of knowledge between sites where we have fossil pollen data from, and create a more complete picture of the past. Good level of agreement between model and pollen data where they overlapped in space further validated our model performance.
Once the model was tested and validated for the region, it became possible to probe one of the long standing questions regarding East African vegetation: How did East Africa lose its tropical forests? The present-day vegetation in the tropics is mainly characterized by continuous forests worldwide except in tropical East Africa, where forests only occur as patches. In a series of simulation experiments, I was able to show under which conditions these forest patches could have been connected and fragmented in the past. This study showed the sensitivity of East African vegetation to climate change and variability such as those expected under future climate change.
El Niño Southern Oscillation (ENSO) events that result from the fluctuations in temperature between the ocean and atmosphere, bring further variability to East African climate and are predicted to increase in intensity in the future. But climate models are still not good at capturing the pattens of these events. In a study where I quantified the influence of ENSO events on East African vegetation, I showed how different the future vegetation could be from what we currently predict with these climate models that lack accurate ENSO contribution. Consideration of these discrepancies is important for our future global carbon budget calculations and management decisions.
Ferroic materials have attracted a lot of attention over the years due to their wide range of applications in sensors, actuators, and memory devices. Their technological applications originate from their unique properties such as ferroelectricity and piezoelectricity. In order to optimize these materials, it is necessary to understand the coupling between their nanoscale structure and transient response, which are related to the atomic structure of the unit cell.
In this thesis, synchrotron X-ray diffraction is used to investigate the structure of ferroelectric thin film capacitors during application of a periodic electric field. Combining electrical measurements with time-resolved X-ray diffraction on a working device allows for visualization of the interplay between charge flow and structural motion. This constitutes the core of this work. The first part of this thesis discusses the electrical and structural dynamics of a ferroelectric Pt/Pb(Zr0.2,Ti0.8)O3/SrRuO3 heterostructure during charging, discharging, and polarization reversal. After polarization reversal a non-linear piezoelectric response develops on a much longer time scale than the RC time constant of the device. The reversal process is inhomogeneous and induces a transient disordered domain state. The structural dynamics under sub-coercive field conditions show that this disordered domain state can be remanent and can be erased with an appropriate voltage pulse sequence. The frequency-dependent dynamic characterization of a Pb(Zr0.52,Ti0.48)O3 layer, at the morphotropic phase boundary, shows that at high frequency, the limited domain wall velocity causes a phase lag between the applied field and both the structural and electrical responses. An external modification of the RC time constant of the measurement delays the switching current and widens the electromechanical hysteresis loop while achieving a higher compressive piezoelectric strain within the crystal.
In the second part of this thesis, time-resolved reciprocal space maps of multiferroic BiFeO3 thin films were measured to identify the domain structure and investigate the development of an inhomogeneous piezoelectric response during the polarization reversal. The presence of 109° domains is evidenced by the splitting of the Bragg peak.
The last part of this work investigates the effect of an optically excited ultrafast strain or heat pulse propagating through a ferroelectric BaTiO3 layer, where we observed an additional current response due to the laser pulse excitation of the metallic bottom electrode of the heterostructure.
In this thesis, we discuss the characterization of orthogroups by so-called disjunctions of identities. The orthogroups are a subclass of the class of completely regular semigroups, a generalization of the concept of a group. Thus there is for all elements of an orthogroup some kind of an inverse element such that both elements commute. Based on a fundamental result by A.H. Clifford, every completely regular semigroup is a semilattice of completely simple semigroups. This allows the description the gross structure of such semigroup. In particular every orthogroup is a semilattice of rectangular groups which are isomorphic to direct products of rectangular bands and groups. Semilattices of rectangular groups coming from various classes are characterized using the concept of an alternative variety, a generalization of the classical idea of a variety by Birkhoff.
After starting with some fundamental definitions and results concerning semigroups, we introduce the concept of disjunctions of identities and summarize some necessary properties. In particular we present some disjunction of identities which is sufficient for a semigroup for being completely regular. Furthermore we derive from this identity some statements concerning Rees matrix semigroups, a possible representation of completely simple semigroups. A main result of this thesis is the general description of disjunctions of identities such that a completely regular semigroup satisfying the described identity is a semilattice of left groups (right groups / groups). In this case the completely regular semigroup is an orthogroup. Furthermore we define various classes of rectangular groups such that there is an exponent taken from a set of pairwise coprime positive integers. An important result is the characterization of the class of all semilattices of particular rectangular groups (taken from the classes defined before) using a set-theoretic minimal set of disjunctions of identities. Additionally we investigate semilattices of groups (so-called Clifford semigroups). For this purpose we consider abelian groups of particular exponents and prove some well-known results from the theory of Clifford semigroups in an alternative way applying the concept of disjunctions of identities. As a practical application of the results concerning semilattices of left zero semigroups and right zero semigroups we identify a particular transformation semigroup. For more detailed information about the product of two arbitrary elements of a semilattice of semigroups we introduce the concept of strong semilattices of semigroups. It is well-known that a semilattice of groups is a strong semilattice of groups. So we can characterize a strong semilattice of groups of particular pairwise coprime exponents by disjunctions of identities. Additionally we describe the class of all strong semilattices of left zero semigroups and right zero semigroups with the help of such kind of identity, and we relate this statement to the theory of normal bands. A possible extension of the already described semilattices of rectangular groups can be achieved by an auxiliary total order (in terms of chains of semigroups). To this end we present a corresponding characterization due to disjunctions of identities which is obviously minimal. A list of open questions which have arisen during the research for this thesis, but left crude, is attached.
Synthesis of artificial building blocks for sortase-mediated ligation and their enzymatic linkage
(2018)
The enzyme Sortase A catalyzes the formation of a peptide bond between the recognition sequence LPXTG and an oligoglycine. While manifold ligations between proteins and various biomolecules, proteins and small synthetic molecules as well as proteins and surfaces have been reported, the aim of this thesis was to investigate the sortase-catalyzed linkage between artificial building blocks. Hence, this could pave the way for the use of sortase A for tasks from a chemical point of view and maybe even materials science.
For the proof of concept, the studied systems were kept as simple as possible at first by choosing easily accessible silica NPs and commercially available polymers. These building blocks were functionalized with peptide motifs for sortase-mediated ligation. Silica nanoparticles were synthesized with diameters of 60 and 200 nm and surface modified with C=C functionalities. Then, peptides bearing a terminal cysteine were covalently linked by means of a thiol-ene reaction. 60 nm SiO2 NPs were functionalized with pentaglycines, while peptides with LPETG motif were linked to 200 nm silica particles. Polyethyleneglycol (PEG) and poly(N isopropylacrylamide) (PNIPAM) were likewise functionalized with peptides by thiol-ene reaction between cysteine residues and C=C units in the polymer end groups. Hence, G5-PEG and PNIPAM-LPETG conjugates were obtained. With this set of building blocks, NP–polymer hybrids, NP–NP, and polymer–polymer structures were generated by sortase-mediated ligation and the product formation shown by transmission electron microscopy, MALDI-ToF mass spectrometry and dynamic light scatting, among others. Thus, the linkage of these artificial building blocks by the enzyme sortase A could be demonstrated.
However, when using commercially available polymers, the purification of the polymer–peptide conjugates was impossible and resulted in a mixture containing unmodified polymer. Therefore, strategies were developed for the own synthesis of pure peptide-polymer and polymer-peptide conjugates as building blocks for sortase-mediated ligation. The designed routes are based on preparing polymer blocks via RAFT polymerization from CTAs that are attached to N- or C-terminus, respectively, of a peptide. GG-PNIPAM was synthesized through attachment of a suitable RAFT CTA to Fmoc-GG in an esterification reaction, followed by polymerization of NIPAM and cleavage of the Fmoc protection group. Furthermore, several peptides were synthesized by solid-phase peptide synthesis. The linkage of a RAFT CTA (or
polymerization initiator) to the N-terminus of a peptide can be conducted in an automated fashion as last step in a peptide synthesizer. The synthesis of such a conjugate couldn’t be realized in the time frame of this thesis, but many promising strategies exist to continue this strategy using different coupling reagents. Such polymer building blocks can be used to synthesize protein-polymer conjugates catalyzed by sortase A and the approach can be carried on to the synthesis of block copolymers by using polymer blocks with peptide motifs on both ends.
Although the proof of concept demonstrated in this thesis only shows examples that can be also synthesized by exclusively chemical techniques, a toolbox of such building blocks will enable the future formation of new materials and pave the way for the application of enzymes in materials science. In addition to nanoparticle systems and block copolymers, this also includes combination with protein-based building blocks to form hybrid materials. Hence, sortase could become an enzymatic tool that complements established chemical linking technologies and provides specific peptide motifs that are orthogonal to all existing chemical functional groups.
Spectroscopy at the limit
(2018)
Thematic role assignment and word order preferences in the child language acquisition of Tagalog
(2018)
A critical task in daily communications is identifying who did what to whom in an utterance, or assigning the thematic roles agent and patient in a sentence. This dissertation is concerned with Tagalog-speaking children’s use of word order and morphosyntactic markers for thematic role assignment. It aims to explain children’s difficulties in interpreting sentences with a non-canonical order of arguments (i.e., patient-before-agent) by testing the predictions of the following accounts: the frequency account (Demuth, 1989), the Competition model (MacWhinney & Bates, 1989), and the incremental processing account (Trueswell & Gleitman, 2004). Moreover, the experiments in this dissertation test the influence of a word order strategy in a language like Tagalog, where the thematic roles are always unambiguous in a sentence, due to its verb-initial order and its voice-marking system. In Tagalog’s voice-marking system, the inflection on the verb indicates the thematic role of the noun marked by 'ang.' First, the possible basis for a word order strategy in Tagalog was established using a sentence completion experiment given to adults and 5- and 7-year-old children (Chapter 2) and a child-directed speech corpus analysis (Chapter 3). In general, adults and children showed an agent-before-patient preference, although adults’ preference was also affected by sentence voice. Children’s comprehension was then examined through a self-paced listening and picture verification task (Chapter 3) and an eye-tracking and picture selection task (Chapter 4), where word order (agent-initial or patient-initial) and voice (agent voice or patient voice) were manipulated. Offline (i.e., accuracy) and online (i.e., listening times, looks to the target) measures revealed that 5- and 7-year-old Tagalog-speaking children had a bias to interpret the first noun as the agent. Additionally, the use of word order and morphosyntactic markers was found to be modulated by voice. In the agent voice, children relied more on a word order strategy; while in the patient voice, they relied on the morphosyntactic markers. These results are only partially explained by the accounts being tested in this dissertation. Instead, the findings support computational accounts of incremental word prediction and learning such as Chang, Dell, & Bock’s (2006) model.
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.
Various ways of preparing enantiomerically pure 2-amino[6]helicene derivatives were explored. Ni(0) mediated cyclotrimerization of enantiopure triynes provided (M)- and (P)-7,8-bis(p-tolyl)hexahelicene-2-amine in >99% ee as well as its benzoderivative in >99% ee. The stereocontrol was found to be inefficient for a 2- aminobenzo[6]helicene congener with an embedded five-membered ring. Helically chiral imidazolium salts bearing one or two helicene moieties have been synthesized and applied in enantioselective [2+2+2] cyclotrimerization catalyzed by an in situ formed Ni(0)-NHC complex. The synthesis of the first helically chiral Pd- and Ru-NHC complexes and their application in enantioselective catalysis was demonstrated. The latter shows promising results in enantioselective olefin metathesis reactions. A mechanistic proposal for asymmetric ring closing metathesis is provided.
Eta Carinae
(2018)
The exceptional binary star Eta Carinae has been fascinating scientists and the people in the Southern hemisphere alike for hundreds of years. It survived an enormous outbreak, comparable to a supernova energy-wise, and for a short period became the brightest star of the night sky. From observations from the radio regime to X-rays the system's characteristics and its emission in photon energies up to ~ 50 keV are well studied today. The binary is composed of two massive stars of ~ 30 and ~ 100 solar masses. Either star drives a strong stellar wind that continuously carries away a fraction of its mass. The collision of these winds leads to a shock on each side of the encounter. In the wind-wind-collision region plasma gets heated when it is overrun by the shocks. Part of the emission seen in X-rays can be attributed to this plasma. Above ~ 50 keV the emission is no longer of thermal origin: the required plasma temperature exceeds the available mechanical energy input of the stellar winds. In contrast to its observational history in thermal energies observational evidence of Eta Carinae's non-thermal emission has only recently built up. In high-energy gamma-rays Eta Carinae is the only binary of its kind that has been detected unambiguously. Its energy spectrum reaches up to ~ hundred GeV, a regime where satellite-based gamma-ray experiments run out of statistics. Ground-based gamma-ray experiments have the advantage of large photon collection areas. H.E.S.S. is the only gamma-ray experiment located in the Southern hemisphere and thus able to observe Eta Carinae in this energy range. H.E.S.S. measures gamma-rays via electromagnetic showers of particles that very-high-energy gamma-rays initiate in the atmosphere. The main challenge in observations of Eta Carinae with H.E.S.S. is the UV emission of the Carina nebula that leads to a background that is up to 10 times stronger than usual for H.E.S.S. This thesis presents the first detection of a colliding-wind binary in very-high-energy gamma-rays and documents the studies that led to it. The differential gamma-ray energy spectrum of Eta Carinae is measured up to 700 GeV. A hadronic and leptonic origin of the gamma-ray emission is discussed and based on the comparison of cooling times a hadronic scenario is favoured.
Movement and navigation are essential for many organisms during some parts of their lives. This is also true for bacteria, which can move along surfaces and swim though liquid environments. They are able to sense their environment, and move towards environmental cues in a directed fashion.
These abilities enable microbial lifecyles in biofilms, improved food uptake, host infection, and many more. In this thesis we study aspects of the swimming movement - or motility - of the soil bacterium (P. putida). Like most bacteria, P. putida swims by rotating its helical flagella, but their arrangement differs from the main model organism in bacterial motility research: (E. coli). P. putida is known for its intriguing motility strategy, where fast and slow episodes can occur after each other. Up until now, it was not known how these two speeds can be produced, and what advantages they might confer to this bacterium.
Normally the flagella, the main component of thrust generation in bacteria, are not observable by ordinary light microscopy. In order to elucidate this behavior, we therefore used a fluorescent staining technique on a mutant strain of this species to specifically label the flagella, while leaving the cell body only faintly stained. This allowed us to image the flagella of the swimming bacteria with high spacial and temporal resolution with a customized high speed fluorescence microscopy setup. Our observations show that P. putida can swim in three different modes. First, It can swim with the flagella pushing the cell body, which is the main mode of swimming motility previously known from other bacteria. Second, it can swim with the flagella pulling the cell body, which was thought not to be possible in situations with multiple flagella. Lastly, it can wrap its flagellar bundle around the cell body, which results in a speed wich is slower by a factor of two. In this mode, the flagella are in a different physical conformation with a larger radius so the cell body can fit inside. These three swimming modes explain the previous observation of two speeds, as well as the non strict alternation of the different speeds.
Because most bacterial swimming in nature does not occur in smoothly walled glass enclosures under a microscope, we used an artificial, microfluidic, structured system of obstacles to study the motion of our model organism in a structured environment. Bacteria were observed in microchannels with cylindrical obstacles of different sizes and with different distances with video microscopy and cell tracking. We analyzed turning angles, run times, and run length, which we compared to a minimal model for movement in structured geometries. Our findings show that hydrodynamic interactions with the walls lead to a guiding of the bacteria along obstacles. When comparing the observed behavior with the statics of a particle that is deflected with every obstacle contact, we find that cells run for longer distances than that model.
Navigation in chemical gradients is one of the main applications of motility in bacteria. We studied the swimming response of P. putida cells to chemical stimuli (chemotaxis) of the common food preservative sodium benzoate. Using a microfluidic gradient generation device, we created gradients of varying strength, and observed the motion of cells with a video microscope and subsequent cell tracking. Analysis of different motility parameters like run lengths and times, shows that P. putida employs the classical chemotaxis strategy of E. coli: runs up the gradient are biased to be longer than those down the gradient. Using the two different run speeds we observed due to the different swimming modes, we classify runs into `fast' and `slow' modes with a Gaussian mixture model (GMM). We find no evidence that P. putida's uses its swimming modes to perform chemotaxis.
In most studies of bacterial motility, cell tracking is used to gather trajectories of individual swimming cells. These trajectories then have to be decomposed into run sections and tumble sections. Several algorithms have been developed to this end, but most require manual tuning of a number of parameters, or extensive measurements with chemotaxis mutant strains. Together with our collaborators, we developed a novel motility analysis scheme, based on generalized Kramers-Moyal-coefficients. From the underlying stochastic model, many parameters like run length etc., can be inferred by an optimization procedure without the need for explicit run and tumble classification. The method can, however, be extended to a fully fledged tumble classifier. Using this method, we analyze E. coli chemotaxis measurements in an aspartate analog, and find evidence for a chemotactic bias in the tumble angles.
The scientific drilling campaign PALEOVAN was conducted in the summer of 2010 and was part of the international continental drilling programme (ICDP). The main goal of the campaign was the recovery of a sensitive climate archive in the East of Anatolia. Lacustrine deposits underneath the lake floor of ‘Lake Van’ constitute this archive. The drilled core material was recovered from two locations: the Ahlat Ridge and the Northern Basin. A composite core was constructed from cored material of seven parallel boreholes at the Ahlat Ridge and covers an almost complete lacustrine history of Lake Van. The composite record offered sensitive climate proxies such as variations of total organic carbon, K/Ca ratios, or a relative abundance of arboreal pollen. These proxies revealed patterns that are similar to climate proxy variations from Greenland ice cores. Climate variations in Greenland ice cores have been dated by modelling the timing of orbital forces to affect the climate. Volatiles from melted ice aliquots are often taken as high-resolution proxies and provide a base for fitting the according temporal models.
The ICDP PALEOVAN scientific team fitted proxy data from the lacustrine drilling record to ice core data and constructed an age model. Embedded volcaniclastic layers had to be dated radiometrically in order to provide independent age constraints to the climate-stratigraphic age model. Solving this task by an application of the 40Ar/39Ar method was the main objective of this thesis. Earlier efforts to apply the 40Ar/39Ar dating resulted in inaccuracies that could not be explained satisfactorily.
The absence of K-rich feldspars in suitable tephra layers implied that feldspar crystals needed to be 500 μm in size minimum, in order to apply single-crystal 40Ar/39Ar dating. Some of the samples did not contain any of these grain sizes or only very few crystals of that size. In order to overcome this problem this study applied a combined single-crystal and multi-crystal approach with different crystal fractions from the same sample. The preferred method of a stepwise heating analysis of an aliquot of feldspar crystals has been applied to three samples. The Na-rich crystals and their young geological age required 20 mg of inclusion-free, non-corroded feldspars. Small sample volumes (usually 25 % aliquots of 5 cm3 of sample material – a spoon full of tephra) and the widespread presence of melt-inclusion led to the application of combined single- and multigrain total fusion analyses. 40Ar/39Ar analyses on single crystals have the advantage of being able to monitor the presence of excess 40Ar and detrital or xenocrystic contamination in the samples. Multigrain analyses may hide the effects from these obstacles. The results from the multigrain analyses are therefore discussed with respect to the findings from the respective cogenetic single crystal ages. Some of the samples in this study were dated by 40Ar/39Ar on feldspars on multigrain separates and (if available) in combination with only a few single crystals. 40Ar/39Ar ages from two of the samples deviated statistically from the age model. All other samples resulted in identical ages. The deviations displayed older ages than those obtained from the age model. t-Tests compared radiometric ages with available age control points from various proxies and from the relative paleointensity of the earth magnetic field within a stratigraphic range of ± 10 m. Concordant age control points from different relative chronometers indicated that deviations are a result of erroneous 40Ar/39Ar ages. The thesis argues two potential reasons for these ages: (1) the irregular appearance of 40Ar from rare melt- and fluid- inclusions and (2) the contamination of the samples with older crystals due to a rapid combination of assimilation and ejection.
Another aliquot of feldspar crystals that underwent separation for the application of 40Ar/39Ar dating was investigated for geochemical inhomogeneities. Magmatic zoning is ubiquitous in the volcaniclastic feldspar crystals. Four different types of magmatic zoning were detected. The zoning types are compositional zoning (C-type zoning), pseudo-oscillatory zoning of trace ele- ment concentrations (PO-type zoning), chaotic and patchy zoning of major and trace element concentrations (R-type zoning) and concentric zoning of trace elements (CC-type zoning). Sam- ples that deviated in 40Ar/39Ar ages showed C-type zoning, R-type zoning or a mix of different types of zoning (C-type and PO-type). Feldspars showing PO-type zoning typically represent the smallest grain size fractions in the samples. The constant major element compositions of these crystals are interpreted to represent the latest stages in the compositional evolution of feldspars in a peralkaline melt. PO-type crystals contain less melt- inclusions than other zoning types and are rarely corroded. This thesis concludes that feldspars that show PO-type zoning are most promising chronometers for the 40Ar/39Ar method, if samples provide mixed zoning types of Quaternary anorthoclase feldspars.
Five samples were dated by applying the 40Ar/39Ar method to volcanic glass. High fractions of atmospheric Ar (typically > 98%) significantly hampered the precision of the 40Ar/39Ar ages and resulted in rough age estimates that widely overlap the age model. Ar isotopes indicated that the glasses bore a chorine-rich Ar-end member. The chlorine-derived 38Ar indicated chlorine-rich fluid-inclusions or the hydration of the volcanic glass shards. This indication strengthened the evidence that irregularly distributed melt-inclusions and thus irregular distributed excess 40Ar influenced the problematic feldspar 40Ar/39Ar ages. Whether a connection between a corrected initial 40Ar/36Ar ratio from glasses to the 40Ar/36Ar ratios from pore waters exists remains unclear.
This thesis offers another age model, which is similarly based on the interpolation of the temporal tie points from geophysical and climate-stratigraphic data. The model used a PCHIP- interpolation (piecewise cubic hermite interpolating polynomial) whereas the older age model used a spline-interpolation. Samples that match in ages from 40Ar/39Ar dating of feldspars with the earlier published age model were additionally assigned with an age from the PCHIP- interpolation. These modelled ages allowed a recalculation of the Alder Creek sanidine mineral standard. The climate-stratigraphic calibration of an 40Ar/39Ar mineral standard proved that the age versus depth interpolations from PAELOVAN drilling cores were accurate, and that the applied chronometers recorded the temporal evolution of Lake Van synchronously.
Petrochemical discrimination of the sampled volcaniclastic material is also given in this thesis. 41 from 57 sampled volcaniclastic layers indicate Nemrut as their provenance. Criteria that served for the provenance assignment are provided and reviewed critically. Detailed correlations of selected PALEOVAN volcaniclastics to onshore samples that were described in detail by earlier studies are also discussed. The sampled volcaniclastics dominantly have a thickness of < 40 cm and have been ejected by small to medium sized eruptions. Onshore deposits from these types of eruptions are potentially eroded due to predominant strong winds on Nemrut and Süphan slopes. An exact correlation with the data presented here is therefore equivocal or not possible at all.
Deviating feldspar 40Ar/39Ar ages can possibly be explained by inherited 40Ar from feldspar xenocrysts contaminating the samples. In order to test this hypothesis diffusion couples of Ba were investigated in compositionally zoned feldspar crystals. The diffusive behaviour of Ba in feldspar is known, and gradients in the changing concentrations allowed for the calculation of the duration of the crystal’s magmatic development since the formation of the zoning interface. Durations were compared with degassing scenarios that model the Ar-loss during assimilation and subsequent ejection of the xenocrystals. Diffusive equilibration of the contrasting Ba concentrations is assumed to generate maximum durations as the gradient could have been developed in several growth and heating stages. The modelling does not show any indication of an involvement of inherited 40Ar in any of the deviating samples. However, the analytical set-up represents the lower limit of the required spatial resolution. Therefore, it cannot be excluded that the degassing modelling relies on a significant overestimation of the maximum duration of the magmatic history. Nevertheless, the modelling of xenocrystal degassing evidences that the irregular incorporation of excess 40Ar by melt- and fluid inclusions represents the most critical problem that needs to be overcome in dating volcaniclastic feldspars from the PALEOVAN drill cores. This thesis provides the complete background in generating and presenting 40Ar/39Ar ages that are compared to age data from a climate-stratigraphic model. Deviations are identified statistically and then discussed in order to find explanations from the age model and/or from 40Ar/39Ar geochronology. Most of the PALEOVAN stratigraphy provides several chronometers that have been proven for their synchronicity. Lacustrine deposits from Lake Van represent a key archive for reconstructing climate evolution in the eastern Mediterranean and in the Near East. The PALEOVAN record offers a climate-stratigraphic age model with a remarkable accuracy and resolution.
In this dissertation the lattice and the magnetic recovery dynamics of the two heavy rare-earth metals Dy and Gd after femtosecond photoexcitation are described. For the investigations, thin films of Dy and Gd were measured at low temperatures in the antiferromagnetic phase of Dy and close to room temperature in the ferromagnetic phase of Gd. Two different optical pump-x-ray probe techniques were employed: Ultrafast x-ray diffraction with hard x-rays (UXRD) yields the structural response of heavy rare-earth metals and resonant soft (elastic) x-ray diffraction (RSXD), which allows measuring directly changes in the helical antiferromagnetic order of Dy. The combination of both techniques enables to study the complex interaction between the magnetic and the phononic subsystems.
Microbiota analyses of patients suffering from various diseases suggest a beneficial role of Akkermansia muciniphila in the maintenance of health, whereas several studies in animal models of intestinal inflammation report that this organism may aggravate inflammation. Therefore, it is important to clarify under which circumstances A. muciniphila exerts negative effects in the intestine of its host.
The previously reported observation that A. muciniphila aggravates acute intestinal inflammation in the Salmonella enterica serovar Typhimurium infection mouse model colonized with a simplified human intestinal microbiota was investigated in this study. To unravel the underlying mechanism that led to the observed phenomenon, the time course of events following the infection was analyzed. In mice colonized with a simplified human intestinal microbiota, Salmonella infection induced clear signs of intestinal inflammation three days post infection. The inflammatory response was similar in mice colonized with A. muciniphila before Salmonella infection. These observations were independent of the time when colonization with the simplified human intestinal microbiota occurred, right after birth or only after weaning, and contradict the previous report.
To find out whether A. muciniphila influences the development of chronic intestinal inflammation in a genetically predisposed host, mono-associated interleukin-10-deficient (Il10-/-) mice, Il10-/- mice dual-associated with A. muciniphila and colitogenic Escherichia coli NC101, as well as Il10-/- mice associated with A. muciniphila and a simplified human intestinal microbiota were compared to the respective mice without A. muciniphila. The data clearly show that in these gnotobiotic Il10-/- mice, A. muciniphila neither induces intestinal inflammation itself nor modulates it after induction by a colitogenic bacterium or by a simplified human intestinal microbiota.
The experiments lead to the conclusion that the promotion of intestinal inflammation is not an intrinsic feature of this bacterium. The results of this study encourage the proposed use of A. muciniphila for the prevention or treatment of metabolic disorders.
Physical computing covers the design and realization of interactive objects and installations and allows learners to develop concrete, tangible products of the real world, which arise from their imagination. This can be used in computer science education to provide learners with interesting and motivating access to the different topic areas of the subject in constructionist and creative learning environments. However, if at all, physical computing has so far mostly been taught in afternoon clubs or other extracurricular settings. Thus, for the majority of students so far there are no opportunities to design and create their own interactive objects in regular school lessons.
Despite its increasing popularity also for schools, the topic has not yet been clearly and sufficiently characterized in the context of computer science education. The aim of this doctoral thesis therefore is to clarify physical computing from the perspective of computer science education and to adequately prepare the topic both content-wise and methodologically for secondary school teaching. For this purpose, teaching examples, activities, materials and guidelines for classroom use are developed, implemented and evaluated in schools.
In the theoretical part of the thesis, first the topic is examined from a technical point of view. A structured literature analysis shows that basic concepts used in physical computing can be derived from embedded systems, which are the core of a large field of different application areas and disciplines. Typical methods of physical computing in professional settings are analyzed and, from an educational perspective, elements suitable for computer science teaching in secondary schools are extracted, e. g. tinkering and prototyping. The investigation and classification of suitable tools for school teaching show that microcontrollers and mini computers, often with extensions that greatly facilitate the handling of additional components, are particularly attractive tools for secondary education. Considering the perspectives of science, teachers, students and society, in addition to general design principles, exemplary teaching approaches for school education and suitable learning materials are developed and the design, production and evaluation of a physical computing construction kit suitable for teaching is described.
In the practical part of this thesis, with “My Interactive Garden”, an exemplary approach to integrate physical computing in computer science teaching is tested and evaluated in different courses and refined based on the findings in a design-based research approach. In a series of workshops on physical computing, which is based on a concept for constructionist professional development that is developed specifically for this purpose, teachers are empowered and encouraged to develop and conduct physical computing lessons suitable for their particular classroom settings. Based on their in-class experiences, a process model of physical computing teaching is derived. Interviews with those teachers illustrate that benefits of physical computing, including the tangibility of crafted objects and creativity in the classroom, outweigh possible drawbacks like longer preparation times, technical difficulties or difficult assessment. Hurdles in the classroom are identified and possible solutions discussed.
Empirical investigations in the different settings reveal that “My Interactive Garden” and physical computing in general have a positive impact, among others, on learner motivation, fun and interest in class and perceived competencies.
Finally, the results from all evaluations are combined to evaluate the design principles for physical computing teaching and to provide a perspective on the development of decision-making aids for physical computing activities in school education.
In the present work, we use symbolic regression for automated modeling of dynamical systems. Symbolic regression is a powerful and general method suitable for data-driven identification of mathematical expressions. In particular, the structure and parameters of those expressions are identified simultaneously.
We consider two main variants of symbolic regression: sparse regression-based and genetic programming-based symbolic regression. Both are applied to identification, prediction and control of dynamical systems.
We introduce a new methodology for the data-driven identification of nonlinear dynamics for systems undergoing abrupt changes. Building on a sparse regression algorithm derived earlier, the model after the change is defined as a minimum update with respect to a reference model of the system identified prior to the change. The technique is successfully exemplified on the chaotic Lorenz system and the van der Pol oscillator. Issues such as computational complexity, robustness against noise and requirements with respect to data volume are investigated.
We show how symbolic regression can be used for time series prediction. Again, issues such as robustness against noise and convergence rate are investigated us- ing the harmonic oscillator as a toy problem. In combination with embedding, we demonstrate the prediction of a propagating front in coupled FitzHugh-Nagumo oscillators. Additionally, we show how we can enhance numerical weather predictions to commercially forecast power production of green energy power plants.
We employ symbolic regression for synchronization control in coupled van der Pol oscillators. Different coupling topologies are investigated. We address issues such as plausibility and stability of the control laws found. The toolkit has been made open source and is used in turbulence control applications.
Genetic programming based symbolic regression is very versatile and can be adapted to many optimization problems. The heuristic-based algorithm allows for cost efficient optimization of complex tasks.
We emphasize the ability of symbolic regression to yield white-box models. In contrast to black-box models, such models are accessible and interpretable which allows the usage of established tool chains.
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.
Basaltic fissure eruptions, such as on Hawai'i or on Iceland, are thought to be driven by the lateral propagation of feeder dikes and graben subsidence. Associated solid earth processes, such as deformation and structural development, are well studied by means of geophysical and geodetic technologies. The eruptions themselves, lava fountaining and venting dynamics, in turn, have been much less investigated due to hazardous access, local dimension, fast processes, and resulting poor data availability.
This thesis provides a detailed quantitative understanding of the shape and dynamics of lava fountains and the morphological changes at their respective eruption sites. For this purpose, I apply image processing techniques, including drones and fixed installed cameras, to the sequence of frames of video records from two well-known fissure eruptions in Hawai'i and Iceland. This way I extract the dimensions of multiple lava fountains, visible in all frames. By putting these results together and considering the acquisition times of the frames I quantify the variations in height, width and eruption velocity of the lava fountains. Then I analyse these time-series in both time and frequency domains and investigate the similarities and correlations between adjacent lava fountains. Following this procedure, I am able to link the dynamics of the individual lava fountains to physical parameters of the magma transport in the feeder dyke of the fountains.
The first case study in this thesis focuses on the March 2011 Pu'u'O'o eruption, Hawai'i, where a continuous pulsating behaviour at all eight lava fountains has been observed. The lava fountains, even those from different parts of the fissure that are closely connected, show a similar frequency content and eruption behaviour. The regular pattern in the heights of lava fountain suggests a controlling process within the magma feeder system like a hydraulic connection in the underlying dyke, affecting or even controlling the pulsating behaviour.
The second case study addresses the 2014-2015 Holuhraun fissure eruption, Iceland. In this case, the feeder dyke is highlighted by the surface expressions of graben-like structures and fault systems. At the eruption site, the activity decreases from a continuous line of fire of ~60 vents to a limited number of lava fountains. This can be explained by preferred upwards magma movements through vertical structures of the pre-eruptive morphology. Seismic tremors during the eruption reveal vent opening at the surface and/or pressure changes in the feeder dyke. The evolving topography of the cinder cones during the eruption interacts with the lava fountain behaviour. Local variations in the lava fountain height and width are controlled by the conduit diameter, the depth of the lava pond and the shape of the crater. Modelling of the fountain heights shows that long-term eruption behaviour is controlled mainly by pressure changes in the feeder dyke.
This research consists of six chapters with four papers, including two first author and two co-author papers. It establishes a new method to analyse lava fountain dynamics by video monitoring. The comparison with the seismicity, geomorphologic and structural expressions of fissure eruptions shows a complex relationship between focussed flow through dykes, the morphology of the cinder cones, and the lava fountain dynamics at the vents of a fissure eruption.
Synthesis, assembly and thermo-responsivity of polymer-functionalized magnetic cobalt nanoparticles
(2018)
This thesis mainly covers the synthesis, surface modification, magnetic-field-induced assembly and thermo-responsive functionalization of superparamagnetic Co NPs initially stabilized by hydrophobic small molecules oleic acid (OA) and trioctylphosphine oxide (TOPO), as well as the synthesis of both superparamagnetic and ferromagnetic Co NPs by using end-functionalized-polystyrene as stabilizer.
Co NPs, due to their excellent magnetic and catalytic properties, have great potential application in various fields, such as ferrofluids, catalysis, and magnetic resonance imaging (MRI). Superparamagnetic Co NPs are especially interesting, since they exhibit zero coercivity. They get magnetized in an external magnetic field and reach their saturation magnetization rapidly, but no magnetic moment remains after removal of the applied magnetic field. Therefore, they do not agglomerate in the body when they are used in biomedical applications. Normally, decomposition of metallic precursors at high temperature is one of the most important methods in preparation of monodisperse magnetic NPs, providing tunability in size and shape. Hydrophobic ligands like OA, TOPO and oleylamine are often used to both control the growth of NPs and protect them from agglomeration. The as-prepared magnetic NPs can be used in biological applications as long as they are transferred into water. Moreover, their supercrystal assemblies have the potential for high density data storage and electronic devices. In addition to small molecules, polymers can also be used as surfactants for the synthesis of ferromagnetic and superparamagnetic NPs by changing the reaction conditions. Therefore, chapter 2 gives an overview on the basic concept of synthesis, surface modification and self-assembly of magnetic nanoparticles. Various examples were used to illustrate the recent work.
The hydrophobic Co NPs synthesized with small molecules as surfactants limit their biological applications, which require a hydrophilic or aqueous environment. Surface modification (e.g., ligand exchange) is a general idea for either phase transition or surface-functionalization. Therefore, in chapter 3, a ligand exchange process was conducted to functionalize the surface of Co NPs. PNIPAM is one of the most popular smart polymers and its lower critical solution temperature (LCST) is around 32 °C, with a reversible change in the conformation structure between hydrophobic and hydrophilic. The novel nanocomposites of superparamagnetic Co NPs and thermo-responsive PNIPAM are of great interest. Thus, well-defined superparamagnetic Co NPs were firstly synthesized through the thermolysis of cobalt carbonyl by using OA and TOPO as surfactants. A functional ATRP initiator, containing an amine (as anchoring group) and a 2-bromopropionate group (SI-ATRP initiator), was used to replace the original ligands. This process is rapid and facial for efficient surface functionalization and afterwards the Co NPs can be dispersed into polar solvent DMF without aggregation. FT-IR spectroscopy showed that the TOPO was completely replaced, but a small amount of OA remained on the surface. A TGA measurement allowed the calculation of the grafting density of the initiator as around 3.2 initiator/nm2. Then, the surface-initiated ATRP was conducted for the polymerization of NIPAM on the surface of Co NPs and rendered the nanocomposites water-dispersible. A temperature-dependent dynamic light scattering study showed the aggregation behavior of PNIPAM-coated Co NPs upon heating and this process was proven to be reversible. The combination of superparamagnetic and thermo-responsive properties in these hybrid nanoparticles is promising for future applications e.g. in biomedicine.
In chapter 4, the magnetic-field-induced assembly of superparamagnetic cobalt nanoparticles both on solid substrates and at liquid-air interface was investigated. OA- and TOPO-coated Co NPs were synthesized via the thermolysis of cobalt carbonyl and dispersed into either hexane or toluene. The Co NP dispersion was dropped onto substrates (e.g., TEM grid, silicon wafer) and at liquid-air (water-air or ethylene glycol-air) interface. Due to the attractive dipolar interaction, 1-D chains formed in the presence of an external magnetic field. It is known that the concentration and the strength of the magnetic field can affect the assembly behavior of superparamagnetic Co NPs. Therefore, the influence of these two parameters on the morphology of the assemblies was studied. The formed 1-D chains were shorter and flexible at either lower concentration of the Co NP dispersion or lower strength of the external magnetic field due to thermal fluctuation. However, by increasing either the concentration of the NP dispersion or the strength of the applied magnetic field, these chains became longer, thicker and straighter. The reason could be that a high concentration led to a high fraction of short dipolar chains, and their interaction resulted in longer and thicker chains under applied magnetic field. On the other hand, when the magnetic field increased, the induced moments of the magnetic nanoparticles became larger, which dominated over the thermal fluctuation. Thus, the formed short chains connected to each other and grew in length. Thicker chains were also observed through chain-chain interaction. Furthermore, the induced moments of the NPs tended to direct into one direction with increased magnetic field, thus the chains were straighter. In comparison between the assembly on substrates, at water-air interface and at ethylene glycol-air interface, the assembly of Co NPs in hexane dispersion at ethylene glycol-air interface showed the most regular and homogeneous chain structures due to the better spreading of the dispersion on ethylene glycol subphase than on water subphase and substrates. The magnetic-field-induced assembly of superparamagnetic nanoparticles could provide a powerful approach for applications in data storage and electronic devices.
Chapter 5 presented the synthesis of superparamagnetic and ferromagnetic cobalt nanoparticles through a dual-stage thermolysis of cobalt carbonyl (Co2(CO)8) by using polystyrene as surfactant. The amine end-functionalized polystyrene surfactants with different molecular weight were prepared via atom transfer radical polymerization technique. The molecular weight determination of polystyrene was conducted by gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry techniques. The results showed that, when the molecular weight distribution is low (Mw/Mn < 1.2), the measurement by GPC and MALDI-ToF MS provided nearly similar results. For example, the molecular weight of 10600 Da was obtained by MALDI-ToF MS, while GPC gave 10500 g/mol (Mw/Mn = 1.17). However, if the polymer is poly distributed, MALDI-ToF MS cannot provide an accurate value. This was exemplified for a polymer with a molecular weight of 3130 Da measured by MALDI-TOF MS, while GPC showed 2300 g/mol (Mw/Mn = 1.38). The size, size distribution and magnetic properties of the hybrid particles were different by changing either the molecular weight or concentration of the polymer surfactants. The analysis from TEM characterization showed that the size of cobalt nanoparticles stabilized with polystyrene of lower molecular weight (Mn = 2300 g/mol) varied from 12–22 nm, while the size with middle (Mn = 4500 g/mol) and higher molecular weight (Mn = 10500 g/mol) of polystyrene-coated cobalt nanoparticles showed little change. Magnetic measurements exhibited that the small cobalt particles (12 nm) were superparamagnetic, while larger particles (21 nm) were ferromagnetic and assembled into 1-D chains. The grafting density calculated from thermogravimetric analysis showed that a higher grafting density of polystyrene was obtained with lower molecular weight (Mn = 2300 g/mol) than those with higher molecular weight (Mn = 10500 g/mol). Due to the larger steric hindrance, polystyrene with higher molecular weight cannot form a dense shell on the surface of the nanoparticles, which resulted in a lower grafting density. Wide angle X-ray scattering measurements revealed the epsilon cobalt crystalline phases of both superparamagnetic Co NPs coated with polystyrene (Mn = 2300 g/mol) and ferromagnetic Co NPs coated with polystyrene (Mn = 10500 g/mol). Furthermore, a stability study showed that PS-Co NPs prepared with higher polymer concentration and polymer molecular weight exhibited a better stability.
Over the last decades mechanisms of recognition of morphologically complex words have been extensively examined in order to determine whether all word forms are stored and retrieved from the mental lexicon as wholes or whether they are decomposed into their morphological constituents such as stems and affixes. Most of the research in this domain focusses on English. Several factors have been argued to affect morphological processing including, for instance, morphological structure of a word (e.g., existence of allomorphic stem alternations) and its linguistic nature (e.g., whether it is a derived word or an inflected word form). It is not clear, however, whether processing accounts based on experimental evidence from English would hold for other languages. Furthermore, there is evidence that processing mechanisms may differ across various populations including children, adult native speakers and language learners. Recent studies claim that processing mechanisms could also differ between older and younger adults (Clahsen & Reifegerste, 2017; Reifegerste, Meyer, & Zwitserlood, 2017).
The present thesis examined how properties of the morphological structure, types of linguistic operations involved (i.e., the linguistic contrast between inflection and derivation) and characteristics of the particular population such as older adults (e.g., potential effects of ageing as a result of the cognitive decline or greater experience and exposure of older adults) affect initial, supposedly automatic stages of morphological processing in Russian and German. To this end, a series of masked priming experiments was conducted.
In experiments on Russian, the processing of derived -ost’ nouns (e.g., glupost’ ‘stupidity’) and of inflected forms with and without allomorphic stem alternations in 1P.Sg.Pr. (e.g., igraju – igrat’ ‘to play’ vs. košu – kosit’ ‘to mow’) was examined. The first experiment on German examined and directly compared processing of derived -ung nouns (e.g., Gründung ‘foundation’) and inflected -t past participles (e.g., gegründet ‘founded’), whereas the second one investigated the processing of regular and irregular plural forms (-s forms such as Autos ‘cars’ and -er forms such as Kinder ‘children’, respectively).
The experiments on both languages have shown robust and comparable facilitation effects for derived words and regularly inflected forms without stem changes (-t participles in German, forms of -aj verbs in Russian). Observed morphological priming effects could be clearly distinguished from purely semantic or orthographic relatedness between words. At the same time, we found a contrast between forms with and without allomorphic stem alternations in Russian and regular and irregular forms in German, with significantly more priming for unmarked stems (relative to alternated ones) and significantly more priming for regular (compared) word forms. These findings indicate the relevance of morphological properties of a word for initial stages of processing, contrary to claims made in the literature holding that priming effects are determined by surface form and meaning overlap only. Instead, our findings are more consistent with approaches positing a contrast between combinatorial, rule-based and lexically-stored forms (Clahsen, Sonnenstuhl, & Blevins, 2003).
The doctoral dissertation also addressed the role of ageing and age-related cognitive changes on morphological processing. The results obtained on this research issue are twofold. On the one hand, the data demonstrate effects of ageing on general measures of language performance, i.e., overall longer reaction times and/or higher accuracy rates in older than younger individuals. These findings replicate results from previous studies, which have been linked to the general slowing of processing speed at older age and to the larger vocabularies of older adults. One the other hand, we found that more specific aspects of language processing appear to be largely intact in older adults as revealed by largely similar morphological priming effects for older and younger adults. These latter results indicate that initial stages of morphological processing investigated here by means of the masked priming paradigm persist in older age. One caveat should, however, be noted. Achieving the same performance as a younger individual in a behavioral task may not necessarily mean that the same neural processes are involved. Older people may have to recruit a wider brain network than younger individuals, for example. To address this and related possibilities, future studies should examine older people’s neural representations and mechanisms involved in morphological processing.
Holocene climate variability is generally characterized by low frequency changes than compared to the last glaciations including the Lateglacial. However, there is vast evidence for decadal to centennial scale oscillations and millennial scale climate trends, which are within and beyond a human lifetime perception, respectively. Within the Baltic realm, a transitional zone between oceanic and continental climate influence, the impact of Holocene and Lateglacial climate and environmental change is currently partly understood. This is mainly attributed to the scarcity of well-dated and high-resolution sediment records and to the lacking continuity of already investigated archives.
The aim of this doctoral thesis is to reconstruct Holocene and Late Glacial climate variability on local to (over)regional scales based on varved (annually laminated) sediments from Lake Czechowskie down to annual resolution. This project was carried out within the Virtual Institute for Integrated Climate and Landscape Evolution Analyses (ICLEA) and funded by the Helmholtz Association and the Helmholtz Climate Initiative REKLIM (Regional Climate Change). ICLEA intended to gain a better understanding of climate variability and landscape evolution processes in the Northern Central European lowlands since the last deglaciation. REKLIM Topic 8 “Abrupt climate change derived from proxy data” aims at identifying spatiotemporal patterns of climate variability between e.g. higher and lower latitudes. The main aim of this thesis was (i) to establish a robust chronology based on a multiple dating approach for Lake Czechowskie covering the Late Glacial and Holocene and for the Trzechowskie palaeolake for the Lateglacial, respectively, (ii) to reconstruct past climatic and environmental conditions on centennial to multi-millennial time scales and (iii) to distinguish between local to regional different sediments responses to climate change.
Addressing the first aim, the Lake Czechowskie chronology has been established by a multiple dating approach comprising information from varve counting, tephrochronology, AMS 14C dating of terrestrial plant remains, biostratigraphy and 137Cs activity concentration measurements. Those independent age constraints covering the Lateglacial and the entire Holocene and have been further implemented in a Bayesian age model by using OxCal v.4.2. Thus, even within non-varved sediment intervals, robust chronological information has been used for absolute age determination. The identification of five cryptotephras, of which three are used as unambiguous isochrones, is furthermore a significant improvement of the Czechowskie chronology and currently unique for the Holocene within Poland. The first findings of coexisting early Holocene Hässeldalen and Askja-S cryptotephras within a varved sequence even allowed differential dating between both volcanic ashes and stimulated the discussion of revising the absolute ages of the Askja-S tephra.
The Trzechowskie palaeolake chronology has been established by a multiple dating approach comprising varve counting, tephrochronology, AMS 14C dating of terrestrial plant remains and biostratigraphy, covers the Lateglacial period (Allerød and Younger Dryas) and has been implemented in OxCal v.4.2. Those age constraints allowed regional correlation to other high-resolution climate archives and identifying leads and lags of proxy responses at the onset of the Younger Dryas.
The second aim has been accomplished by detailed micro-facies and geochemical analyses of the Czechowskie sediments for the entire Holocene. Thus, especially micro-facies changes had been linked to enhanced productivity at Lake Czechowskie. Most prominent changes have been recorded at 7.3, 6.5, 4.3 and 2.8 varve kyrs BP and are linked to a stepwise increasing influence of Atlantic air masses. Especially, the mid-Holocene change, which had been widely reported from palaeohydrological records in low latitudes, has been identified and linked to large scale reorganization of atmospheric circulation patterns. Thus, especially long-term changes of climatic and environmental boundary conditions are widely recorded by the Czechowskie sediments. The pronounced response to (multi)millennial scale changes is further corroborated by the lack of clear sediment responses to early Holocene centennial scale climate oscillations (e.g. the Preboreal Oscillation).
However, decadal scale changes at Lake Czechowskie during the most recent period (last 140 years) have been investigated in a lake comparison study. To fulfill the third aim of the doctoral thesis, three lakes in close vicinity to each other have been investigated in order to better distinguish how local, site-specific parameters, may superimpose regional climate driven changes. All lakes haven been unambiguously linked by the Askja AD1875 cryptotephra and independent varve chronologies. As a result, climate warming has only been recorded by sedimentation changes at the smallest and best sheltered lake (Głęboczek), whereas the largest lake (Czechowskie) and the shallowest lake (Jelonek) showed attenuated and less clear sediment responses, respectively. The different responses have been linked to morphological lake characteristics (lake size and depth, catchment area). This study highlights the potential of high-resolution lake comparison for robust proxy based climate reconstructions.
In summary, the doctoral thesis presents a high-resolution sediment record with an underlying age model, which is prerequisite for unprecedented age control down to annual resolution. Sediment proxy based climate reconstructions demonstrate the importance of the Czechowskie sediments for better understanding climate variability in the southern Baltic realm. Case studies showed the clear response on millennial time scale, while decadal scale fluctuations are either less well expressed or superimposed by local, site-specific parameters. The identification of volcanic ash layers is not only used for unambiguous isochrones, those are key tie lines for local to supra regional archive synchronization and establish the Lake Czechowskie as a key climate archive.
Plants are unable to move away from unwanted environments and therefore have to locally adapt to changing conditions. Arabidopsis thaliana (Arabidopsis), a model organism in plant biology, has been able to rapidly colonize a wide spectrum of environments with different biotic and abiotic challenges. In recent years, natural variation in Arabidopsis has shown to be an excellent resource to study genes underlying adaptive traits and hybridization’s impact on natural diversity. Studies on Arabidopsis hybrids have provided information on the genetic basis of hybrid incompatibilities and heterosis, as well as inheritance patterns in hybrids. However, previous studies have focused mainly on global accessions and yet much remains to be known about variation happening within a local growth habitat. In my PhD, I investigated the impact of heterozygosity at a local collection site of Arabidopsis and its role in local adaptation. I focused on two different projects, both including hybrids among Arabidopsis individuals collected around Tübingen in Southern Germany. The first project sought to understand the impact of hybridization on metabolism and growth within a local Arabidopsis collection site. For this, the inheritance patterns in primary and secondary metabolism, together with rosette size of full diallel crosses among seven parents originating from Southern Germany were analyzed. In comparison to primary metabolites, compounds from secondary metabolism were more variable and showed pronounced non-additive inheritance patterns. In addition, defense metabolites, mainly glucosinolates, displayed the highest degree of variation from the midparent values and were positively correlated with a proxy for plant size.
In the second project, the role of ACCELERATED CELL DEATH 6 (ACD6) in the defense response pathway of Arabidopsis necrotic hybrids was further characterized. Allelic interactions of ACD6 have been previously linked to hybrid necrosis, both among global and local Arabidopsis accessions. Hence, I characterized the early metabolic and ionic changes induced by ACD6, together with marker gene expression assays of physiological responses linked to its activation. An upregulation of simple sugars and metabolites linked to non-enzymatic antioxidants and the TCA cycle were detected, together with putrescine and acids linked to abiotic stress responses. Senescence was found to be induced earlier in necrotic hybrids and cytoplasmic calcium signaling was unaffected in response to temperature. In parallel, GFP-tagged constructs of ACD6 were developed.
This work therefore gave novel insights on the role of heterozygosity in natural variation and adaptation and expanded our current knowledge on the physiological and molecular responses associated with ACD6 activation.
In the here presented work we discuss a series of results that are all in one way or another connected to the phenomenon of trapping in black hole spacetimes.
First we present a comprehensive review of the Kerr-Newman-Taub-NUT-de-Sitter family of black hole spacetimes and their most important properties. From there we go into a detailed analysis of the bahaviour of null geodesics in the exterior region of a sub-extremal Kerr spacetime. We show that most well known fundamental properties of null geodesics can be represented in one plot. In particular, one can see immediately that the ergoregion and trapping are separated in phase space.
We then consider the sets of future/past trapped null geodesics in the exterior region of a sub-extremal Kerr-Newman-Taub-NUT spacetime. We show that from the point of view of any timelike observer outside of such a black hole, trapping can be understood as two smooth sets of spacelike directions on the celestial sphere of the observer. Therefore the topological structure of the trapped set on the celestial sphere of any observer is identical to that in Schwarzschild.
We discuss how this is relevant to the black hole stability problem.
In a further development of these observations we introduce the notion of what it means for the shadow of two observers to be degenerate. We show that, away from the axis of symmetry, no continuous degeneration exists between the shadows of observers at any point in the exterior region of any Kerr-Newman black hole spacetime of unit mass. Therefore, except possibly for discrete changes, an observer can, by measuring the black holes shadow, determine the angular momentum and the charge of the black hole under observation, as well as the observer's radial position and angle of elevation above the equatorial plane. Furthermore, his/her relative velocity compared to a standard observer can also be measured. On the other hand, the black hole shadow does not allow for a full parameter resolution in the case of a Kerr-Newman-Taub-NUT black hole, as a continuous degeneration relating specific angular momentum, electric charge, NUT charge and elevation angle exists in this case.
We then use the celestial sphere to show that trapping is a generic feature of any black hole spacetime.
In the last chapter we then prove a generalization of the mode stability result of Whiting (1989) for the Teukolsky equation for the case of real frequencies. The main result of the last chapter states that a separated solution of the Teukolsky equation governing massless test fields on the Kerr spacetime, which is purely outgoing at infinity, and purely ingoing at the horizon, must vanish. This has the consequence, that for real frequencies, there are linearly independent fundamental solutions of the radial Teukolsky equation which are purely ingoing at the horizon, and purely outgoing at infinity, respectively. This fact yields a representation formula for solutions of the inhomogenous Teukolsky equation, and was recently used by Shlapentokh-Rothman (2015) for the scalar wave equation.
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.
Through IOs' Eyes
(2018)
Is global governance characterized by overlap and fragmentation, or by coordination and harmonization? There are two rather different narratives about the worlds in which international organizations (IOs) live. One way or another, IOs are part of a broader environment and engage in relations with other actors in it. Rather than being detached from their environment, IOs are shaped by and respond to developments taking place within it (e.g., overlap). Thus, the general research interest of this dissertation lies in organizational responses to such environmental developments. Therein, the emphasis is placed on IO positionality, meaning the position of an IO within a “web” of interorganizational relations, or, more precisely, an IO’s position within an organizational field as a specification of the IO environment.
Against this background, the dissertation poses the following research question: How does an IO’s position within an organizational field shape its responses to developments of the field? In that, three subquestions are advanced: Which position does an IO occupy within the organizational field? How does an IO perceive the organizational field? How does an IO respond to developments and features of the field? Theoretically, the dissertation combines an open system perspective on IOs with two variants of field theory inspired by Bourdieu and by DiMaggio and Powell. Building on the central concept of the organizational field, the dissertation understands IOs as actors with agency. Empirically, the dissertation consists of a qualitative, comparative study and analyzes two IOs located within the organizational field of global food security governance. I select IOs that occupy different positions within the field of food security governance, namely an IO at the core of the field (the United Nations Food and Agriculture Organization, or FAO) and an IO at the periphery of the field (the United Nations Industrial Development Organization, or UNIDO). I compare and analyze their respective perceptions of the field of food security governance, including their own role and their understandings of food security, and their responses over time. To investigate these IOs’ perceptions and responses over time, the method of choice consists of a qualitative content analysis of a wide range of organizational documents (e.g., governing bodies’ reports).
The main argument this dissertation advances is as follows: The position that an IO occupies within an organizational field influences how the organization perceives its environment—in particular, features of and developments within this environment. Against this background, the main findings of this dissertation are as follows: Overall, FAO and UNIDO both perceive proliferation, overlap, and duplication as relevant developments of the organizational field of global food security governance over time. While both IOs see developments in the field of food security governance (e.g., overlap and duplication) as problematic given their detrimental effects for food security governance, FAO and UNIDO differ in decisive regards. Whereas FAO holds a narrative that other actors were responsible for this state of affairs, and thus responsible for reducing or even eliminating overlap and duplication, UNIDO perceives these developments differently. UNIDO acknowledges its own role in the development of overlap and duplication, and therefore also sees a role for itself in addressing these developments. The two IOs thus differ in what they understand to be the causes and historical priors of field-specific developments. Furthermore, while both FAO and UNIDO attempt to demonstrate that they are constructive players within the UN development system, the two IOs differ in their responses: While FAO engages in balancing by voicing its commitment to UN processes and to coordination, yet early on making different reservations, UNIDO, in contrast, engages in UN processes without similar reservations. Accordingly, the two IOs also differ on the responses they employ to field-level harmonization demands.
The dissertation makes several contributions. Theoretically, I contribute an innovative argument on the influence of perceptions for organizational responses to developments in the IOs’ environment. This argument may help us to better understand how IOs as actors embedded within an organizational field deal with changes evolving within these fields. Empirically, I scrutinize developments in food security governance, such as proliferation and overlap, through the eyes of IOs in the field. While proliferation, overlap, and duplication are often referred to in academic debates on food security governance, we do not yet actually understand these phenomena very well. To this, I contribute a study that analyzes IO perceptions of these developments in the field, thus resulting in a more in-depth and nuanced picture of how IOs perceive these developments as a central type of actor in food security governance. Next, to this emphasis on the IO perspective, I also inductively develop a spectrum of IO responses to field developments, ranging from expanding scope to defending turf. Finally, I also make a methodological-conceptual contribution: While concepts such as “position” are well-known, they are sometimes drawn on without developing a clear foundation of how to assess different positions. I thus add an approach for bringing this concept of position to life by developing a range of criteria that can be used to approximate an IO’s position within an organizational field, depending on different types of capital.
More than a billion people rely on water from rivers sourced in High Mountain Asia (HMA), a significant portion of which is derived from snow and glacier melt. Rural communities are heavily dependent on the consistency of runoff, and are highly vulnerable to shifts in their local environment brought on by climate change. Despite this dependence, the impacts of climate change in HMA remain poorly constrained due to poor process understanding, complex terrain, and insufficiently dense in-situ measurements.
HMA's glaciers contain more frozen water than any region outside of the poles. Their extensive retreat is a highly visible and much studied marker of regional and global climate change. However, in many catchments, snow and snowmelt represent a much larger fraction of the yearly water budget than glacial meltwaters. Despite their importance, climate-related changes in HMA's snow resources have not been well studied.
Changes in the volume and distribution of snowpack have complex and extensive impacts on both local and global climates. Eurasian snow cover has been shown to impact the strength and direction of the Indian Summer Monsoon -- which is responsible for much of the precipitation over the Indian Subcontinent -- by modulating earth-surface heating. Shifts in the timing of snowmelt have been shown to limit the productivity of major rangelands, reduce streamflow, modify sediment transport, and impact the spread of vector-borne diseases. However, a large-scale regional study of climate impacts on snow resources had yet to be undertaken.
Passive Microwave (PM) remote sensing is a well-established empirical method of studying snow resources over large areas. Since 1987, there have been consistent daily global PM measurements which can be used to derive an estimate of snow depth, and hence snow-water equivalent (SWE) -- the amount of water stored in snowpack. The SWE estimation algorithms were originally developed for flat and even terrain -- such as the Russian and Canadian Arctic -- and have rarely been used in complex terrain such as HMA.
This dissertation first examines factors present in HMA that could impact the reliability of SWE estimates. Forest cover, absolute snow depth, long-term average wind speeds, and hillslope angle were found to be the strongest controls on SWE measurement reliability. While forest density and snow depth are factors accounted for in modern SWE retrieval algorithms, wind speed and hillslope angle are not. Despite uncertainty in absolute SWE measurements and differences in the magnitude of SWE retrievals between sensors, single-instrument SWE time series were found to be internally consistent and suitable for trend analysis.
Building on this finding, this dissertation tracks changes in SWE across HMA using a statistical decomposition technique. An aggregate decrease in SWE was found (10.6 mm/yr), despite large spatial and seasonal heterogeneities. Winter SWE increased in almost half of HMA, despite general negative trends throughout the rest of the year. The elevation distribution of these negative trends indicates that while changes in SWE have likely impacted glaciers in the region, climate change impacts on these two pieces of the cryosphere are somewhat distinct.
Following the discussion of relative changes in SWE, this dissertation explores changes in the timing of the snowmelt season in HMA using a newly developed algorithm. The algorithm is shown to accurately track the onset and end of the snowmelt season (70% within 5 days of a control dataset, 89% within 10). Using a 29-year time series, changes in the onset, end, and duration of snowmelt are examined. While nearly the entirety of HMA has experienced an earlier end to the snowmelt season, large regions of HMA have seen a later start to the snowmelt season. Snowmelt periods have also decreased in almost all of HMA, indicating that the snowmelt season is generally shortening and ending earlier across HMA.
By examining shifts in both the spatio-temporal distribution of SWE and the timing of the snowmelt season across HMA, we provide a detailed accounting of changes in HMA's snow resources. The overall trend in HMA is towards less SWE storage and a shorter snowmelt season. However, long-term and regional trends conceal distinct seasonal, temporal, and spatial heterogeneity, indicating that changes in snow resources are strongly controlled by local climate and topography, and that inter-annual variability plays a significant role in HMA's snow regime.
Metamaterial devices
(2018)
Digital fabrication machines such as 3D printers excel at producing arbitrary shapes, such as for decorative objects. In recent years, researchers started to engineer not only the outer shape of objects, but also their internal microstructure. Such objects, typically based on 3D cell grids, are known as metamaterials. Metamaterials have been used to create materials that, e.g., change their volume, or have variable compliance.
While metamaterials were initially understood as materials, we propose to think of them as devices.
We argue that thinking of metamaterials as devices enables us to create internal structures that offer functionalities to implement an input-process-output model without electronics, but purely within the material’s internal structure. In this thesis, we investigate three aspects of such metamaterial devices that implement parts of the input-process-output model: (1) materials that process analog inputs by implementing mechanisms based on their microstructure, (2) that process digital signals by embedding mechanical computation into the object’s microstructure, and (3) interactive metamaterial objects that output to the user by changing their outside to interact with their environment. The input to our metamaterial devices is provided directly by the users interacting with the device by means of physically pushing the metamaterial, e.g., turning a handle, pushing a button, etc.
The design of such intricate microstructures, which enable the functionality of metamaterial devices, is not obvious. The complexity of the design arises from the fact that not only a suitable cell geometry is necessary, but that additionally cells need to play together in a well-defined way. To support users in creating such microstructures, we research and implement interactive design tools. These tools allow experts to freely edit their materials, while supporting novice users by auto-generating cells assemblies from high-level input. Our tools implement easy-to-use interactions like brushing, interactively simulate the cell structures’ deformation directly in the editor, and export the geometry as a 3D-printable file. Our goal is to foster more research and innovation on metamaterial devices by allowing the broader public to contribute.
How can interactive devices connect with users in the most immediate and intimate way? This question has driven interactive computing for decades. Throughout the last decades, we witnessed how mobile devices moved computing into users’ pockets, and recently, wearables put computing in constant physical contact with the user’s skin. In both cases moving the devices closer to users allowed devices to sense more of the user, and thus act more personal. The main question that drives our research is: what is the next logical step?
Some researchers argue that the next generation of interactive devices will move past the user’s skin and be directly implanted inside the user’s body. This has already happened in that we have pacemakers, insulin pumps, etc. However, we argue that what we see is not devices moving towards the inside of the user’s body, but rather towards the body’s biological “interface” they need to address in order to perform their function.
To implement our vision, we created a set of devices that intentionally borrow parts of the user’s body for input and output, rather than adding more technology to the body.
In this dissertation we present one specific flavor of such devices, i.e., devices that borrow the user’s muscles. We engineered I/O devices that interact with the user by reading and controlling muscle activity. To achieve the latter, our devices are based on medical-grade signal generators and electrodes attached to the user’s skin that send electrical impulses to the user’s muscles; these impulses then cause the user’s muscles to contract.
While electrical muscle stimulation (EMS) devices have been used to regenerate lost motor functions in rehabilitation medicine since the 1960s, in this dissertation, we propose a new perspective: EMS as a means for creating interactive systems.
We start by presenting seven prototypes of interactive devices that we have created to illustrate several benefits of EMS. These devices form two main categories: (1) Devices that allow users eyes-free access to information by means of their proprioceptive sense, such as the value of a variable in a computer system, a tool, or a plot; (2) Devices that increase immersion in virtual reality by simulating large forces, such as wind, physical impact, or walls and heavy objects.
Then, we analyze the potential of EMS to build interactive systems that miniaturize well and discuss how they leverage our proprioceptive sense as an I/O modality. We proceed by laying out the benefits and disadvantages of both EMS and mechanical haptic devices, such as exoskeletons.
We conclude by sketching an outline for future research on EMS by listing open technical, ethical and philosophical questions that we left unanswered.
The prediction of the ground shaking that can occur at a site of interest due to an earthquake is crucial in any seismic hazard analysis. Usually, empirically derived ground-motion prediction equations (GMPEs) are employed within a logic-tree framework to account for this step. This is, however, challenging if the area under consideration has only low seismicity and lacks enough recordings to develop a region-specific GMPE. It is then usual practice to adapt GMPEs from data-rich regions (host area) to the area with insufficient ground-motion recordings (target area). Host GMPEs must be adjusted in such a way that they will capture the specific ground-motion characteristics of the target area. In order to do so, seismological parameters of the target region have to be provided as, for example, the site-specific attenuation factor kappa0. This is again an intricate task if data amount is too sparse to derive these parameters.
In this thesis, I explore methods that can facilitate the selection of non-endemic GMPEs in a logic-tree analysis or their adjustment to a data-poor region. I follow two different strategies towards this goal.
The first approach addresses the setup of a ground-motion logic tree if no indigenous GMPE is available. In particular, I propose a method to derive an optimized backbone model that captures the median ground-motion characteristics in the region of interest. This is done by aggregating several foreign GMPEs as weighted components of a mixture model in which the weights are inferred from observed data. The approach is applied to Northern Chile, a region for which no indigenous GMPE existed at the time of the study. Mixture models are derived for interface and intraslab type events using eight subduction zone GMPEs originating from different parts of the world. The derived mixtures provide satisfying results in terms of average residuals and average sample log-likelihoods. They outperform all individual non-endemic GMPEs and are comparable to a regression model that was specifically derived for that area.
The second approach is concerned with the derivation of the site-specific attenuation factor kappa0. kappa0 is one of the key parameters in host-to-target adjustments of GMPEs but is hard to derive if data amount is sparse. I explore methods to estimate kappa0 from ambient seismic noise. Seismic noise is, in contrast to earthquake recordings, continuously available. The rapidly emerging field of seismic interferometry gives the possibility to infer velocity and attenuation information from the cross-correlation or deconvolution of long noise recordings. The extraction of attenuation parameters from diffuse wavefields is, however, not straightforward especially not for frequencies above 1 Hz and at shallow depth. In this thesis, I show the results of two studies. In the first one, data of a small-scale array experiment in Greece are used to derive Love wave quality factors in
the frequency range 1-4 Hz. In a second study, frequency dependent quality factors of S-waves (5-15 Hz) are estimated by deconvolving noise recorded in a borehole and at a co-located surface station in West Bohemia/Vogtland. These two studies can be seen as preliminary steps towards the estimation of kappa0 from seismic noise.
Human actuation
(2018)
Ever since the conception of the virtual reality headset in 1968, many researchers have argued that the next step in virtual reality is to allow users to not only see and hear, but also feel virtual worlds. One approach is to use mechanical equipment to provide haptic feedback, e.g., robotic arms, exoskeletons and motion platforms. However, the size and the weight of such mechanical equipment tends to be proportional to its target’s size and weight, i.e., providing human-scale haptic feedback requires human-scale equipment, often restricting them to arcades and lab environments.
The key idea behind this dissertation is to bypass mechanical equipment by instead leveraging human muscle power. We thus create software systems that orchestrate humans in doing such mechanical labor—this is what we call human actuation. A potential benefit of such systems is that humans are more generic, flexible, and versatile than machines. This brings a wide range of haptic feedback to modern virtual reality systems.
We start with a proof-of-concept system—Haptic Turk, focusing on delivering motion experiences just like a motion platform. All Haptic Turk setups consist of a user who is supported by one or more human actuators. The user enjoys an interactive motion simulation such as a hang glider experience, but the motion is generated by those human actuators who manually lift, tilt, and push the user’s limbs or torso. To get the timing and force right, timed motion instructions in a format familiar from rhythm games are generated by the system.
Next, we extend the concept of human actuation from 3-DoF to 6-DoF virtual reality where users have the freedom to walk around. TurkDeck tackles this problem by orchestrating a group of human actuators to reconfigure a set of passive props on the fly while the user is progressing in the virtual environment. TurkDeck schedules human actuators by their distances from the user, and instructs them to reconfigure the props to the right place on the right time using laser projection and voice output.
Our studies in Haptic Turk and TurkDeck showed that human actuators enjoyed the experience but not as much as users. To eliminate the need of dedicated human actuators, Mutual Turk makes everyone a user by exchanging mechanical actuation between two or more users. Mutual Turk’s main functionality is that it orchestrates the users so as to actuate props at just the right moment and with just the right force to produce the correct feedback in each other's experience.
Finally, we further eliminate the need of another user, making human actuation applicable to single-user experiences. iTurk makes the user constantly reconfigure and animate otherwise passive props. This allows iTurk to provide virtual worlds with constantly varying or even animated haptic effects, even though the only animate entity present in the system is the user. Our demo experience features one example each of iTurk’s two main types of props, i.e., reconfigurable props (the foldable board from TurkDeck) and animated props (the pendulum).
We conclude this dissertation by summarizing the findings of our explorations and pointing out future directions. We discuss the development of human actuation compare to traditional machine actuation, the possibility of combining human and machine actuators and interaction models that involve more human actuators.
Plant-derived Transcription Factors for Orthologous Regulation of Gene Expression in the Yeast Saccharomyces cerevisiae
Control of gene expression by transcription factors (TFs) is central in many synthetic biology projects where tailored expression of one or multiple genes is often needed. As TFs from evolutionary distant organisms are unlikely to affect gene expression in a host of choice, they represent excellent candidates for establishing orthogonal control systems. To establish orthogonal regulators for use in yeast (Saccharomyces cerevisiae), we chose TFs from the plant Arabidopsis thaliana. We established a library of 106 different combinations of chromosomally integrated TFs, activation domains (yeast GAL4 AD, herpes simplex virus VP64, and plant EDLL) and synthetic promoters harbouring cognate cis-regulatory motifs driving a yEGFP reporter. Transcriptional output of the different driver / reporter combinations varied over a wide spectrum, with EDLL being a considerably stronger transcription activation domain in yeast, than the GAL4 activation domain, in particular when fused to Arabidopsis NAC TFs. Notably, the strength of several NAC - EDLL fusions exceeded that of the strong yeast TDH3 promoter by 6- to 10-fold. We furthermore show that plant TFs can be used to build regulatory systems encoded by centromeric or episomal plasmids. Our library of TF – DNA-binding site combinations offers an excellent tool for diverse synthetic biology applications in yeast.
COMPASS: Rapid combinatorial optimization of biochemical pathways based on artificial transcription factors
We established a high-throughput cloning method, called COMPASS for COMbinatorial Pathway ASSembly, for the balanced expression of multiple genes in Saccharomyces cerevisiae. COMPASS employs orthogonal, plant-derived artificial transcription factors (ATFs) for controlling the expression of pathway genes, and homologous recombination-based cloning for the generation of thousands of individual DNA constructs in parallel. The method relies on a positive selection of correctly assembled pathway variants from both, in vivo and in vitro cloning procedures. To decrease the turnaround time in genomic engineering, we equipped COMPASS with multi-locus CRISPR/Cas9-mediated modification capacity. In its current realization, COMPASS allows combinatorial optimization of up to ten pathway genes, each transcriptionally controlled by nine different ATFs spanning a 10-fold difference in expression strength. The application of COMPASS was demonstrated by generating cell libraries producing beta-carotene and co-producing beta-ionone and biosensor-responsive naringenin. COMPASS will have many applications in other synthetic biology projects that require gene expression balancing.
CaPRedit: Genome editing using CRISPR-Cas9 and plant-derived transcriptional regulators for the redirection of flux through the FPP branch-point in yeast. Technologies developed over the past decade have made Saccharomyces cerevisiae a promising platform for production of different natural products. We developed CRISPR/Ca9- and plant derived regulator-mediated genome editing approach (CaPRedit) to greatly accelerate strain modification and to facilitate very low to very high expression of key enzymes using inducible regulators. CaPRedit can be implemented to enhance the production of yeast endogenous or heterologous metabolites in the yeast S. cerevisiae. The CaPRedit system aims to faciltiate modification of multiple targets within a complex metabolic pathway through providing new tools for increased expression of genes encoding rate-limiting enzymes, decreased expression of essential genes, and removed expression of competing pathways. This approach is based on CRISPR/Cas9-mediated one-step double-strand breaks to integrate modules containing IPTG-inducible plant-derived artificial transcription factor and promoter pair(s) in a desired locus or loci. Here, we used CaPRedit to redirect the yeast endogenous metabolic flux toward production of farnesyl diphosphate (FPP), a central precursor of nearly all yeast isoprenoid products, by overexpression of the enzymes lead to produce FPP from glutamate. We found significantly higher beta-carotene accumulation in the CaPRedit-mediated modified strain than in the wild type (WT) strain. More specifically, CaPRedit_FPP 1.0 strain was generated, in which three genes involved in FPP synthesis, tHMG1, ERG20, and GDH2, were inducibly overexpressed under the control of strong plant-derived ATFPs. The beta–carotene accumulated in CaPRedit_FPP 1.0 strain to a level 1.3-fold higher than the previously reported optimized strain that carries the same overexpressed genes (as well as additional genetic modifications to redirect yeast endogenous metabolism toward FPP production). Furthermore, the genetic modifications implemented in CaPRedit_FPP 1.0 strain resulted in only a very small growth defect (growth rate relative to the WT is ~ -0.03).
Polymeric materials, which can perform reversible shape changes after programming, in response to a thermal or electrical stimulation, can serve as (soft) actuating components in devices like artificial muscles, photonics, robotics or sensors. Such polymeric actuators can be realized with hydrogels, liquid crystalline elastomers, electro-active polymers or shape-memory polymers by controlling with stumuli such as heat, light, electrostatic or magnetic field. If the application conditions do not allow the direct heating or electric stimulation of these smart devices, noncontact triggering will be required. Remotely controlled actuation have been reported for liquid crystalline elastomer composites or shape-memory polymer network composites, when a persistent external stress is applied during inductive heating in an alternating magnetic field. However such composites cannot meet the demands of applications requiring remotely controlled free-standing motions of the actuating components.
The current thesis investigates, whether a reprogrammable remotely controlled soft actuator can be realized by magneto-sensitive multiphase shape-memory copolymer network composites containing magnetite nanoparticles as magneto-sensitive multivalent netpoints. A central hypothesis was that a magnetically controlled two-way (reversible bidirectional) shape-memory effect in such nanocomposites can be achieved without application of external stress (freestanding), when the required orientation of the crystallizable actuation domains (ADs) can be ensured by an internal skeleton like structure formed by a second crystallizable phase determing the samples´s geometry, while magneto-sensitive iron oxide nanoparticles covalently integrated in the ADs allow remote temperature control. The polymer matrix of these composites should exhibit a phase-segregated morphology mainly composed of cyrstallizable ADs, whereby a second set of higher melting crystallites can take a skeleton like, geometry determining function (geometry determining domains, GDs) after programming of the composite and in this way the orientation of the ADs is established and maintained during actuation. The working principle for the reversible bidirectional movements in the multiphase shape-memory polymer network composite is related to a melting-induced contraction (MIC) during inductive heating and the crystallization induced elongation (CIE) of the oriented ADs during cooling. Finally, the amount of multivalent magnetosensitive netpoints in such a material should be as low as possible to ensure an adequate overall elasticity of the nanocomposite and at the same time a complete melting of both ADs and GDs via inductive heating, which is mandatory for enabling reprogrammability.
At first, surface decorated iron oxide nanoparticles were synthesized and investigated. The coprecipitation method was applied to synthesize magnetic nanoparticles (mNPs) based on magnetite with size of 12±3 nm and in a next step a ring-opening polymerization (ROP) was utilized for covalent surface modification of such mNPs with oligo(ϵ-caprolactone) (OCL) or oligo(ω-pentadecalactone) (OPDL) via the “grafting from” approach. A successful coating of mNPs with OCL and OPDL was confirmed by differential scanning calorimetry (DSC) experiments showing melting peaks at 52±1 °C for mNP-OCL and 89±1 °C for mNP-OPDL. It was further explored whether two-layered surface decorated mNPs, can be prepared via a second surface-initiated ROP of mNP-OCL or mNP-OPDL with ω-pentadecalactone or ϵ-caprolactone. The observation of two distinct melting transitions in DSC experiments as well as the increase in molecular weight of the detached coatings determined by GPC and 1H-NMR indicated a successful synthesis of the twolayered nanoparticles mNP-OCL-OPDL and mNP-OPDL-OCL. In contrast TEM micrographs revealed a reduction of the thickness of the polymeric coating on the nanoparticles after the second ROP, indicating that the applied synthesis and purification required further optimization.
For evaluating the impact of the dispersion of mNPs within a polymer matrix on the resulting inductive heating capability of composites, plain mNPs as well as OCL coated magnetite nanoparticles (mNP-OCLs) were physically incorporated into crosslinked poly(ε-caprolactone) (PCL) networks. Inductive heating experiments were performed with both networks cPCL/mNP and cPCL/mNP-OCL in an alternating magnetic field (AMF) with a magnetic field strength of H = 30 kA·m-1. Here a bulk temperature of Tbulk = 74±2 °C was achieved for cPCL/mNP-OCL, which was almost 20 °C higher than the melting transition of the PCL-based polymer matrix. In contrast, the composite with plain mNPs could only reach a Tbulk of 48±2 °C, which is not sufficient for a complete melting of all PCL crystallites as required for actuation.
The inductive heating capability of a multiphase copolymer nanocomposite network (designed as soft actuators) containing surface decorated mNPs as covalent netpoints was investigated. Such composite was synthesized from star-shaped OCL and OPDL precursors, as well as mNP-OCLs via reaction with HDI. The weight ratio of OPDL and OCL in the starting reaction mixture was 15/85 (wt%/wt%) and the amount of iron oxide in the nanocomposite was 4 wt%. DSC experiments revealed two well separated melting and crystallization peaks confirming the required phase-segregated morphology in the nanocomposite NC-mNP-OCL. TEM images could illustrate a phase-segregated morphology of the polymer matrix on the microlevel with droplet shaped regions attributed to the OPDL domains dispersed in an OCL matrix. The TEM images could further demonstrate that the nanoparticulate netpoints in NC-mNP-OCL were almost homogeneously dispersed within the OCL domains. The tests of the inductive heating capability of the nanocomposites at a magnetic field strength of Hhigh = 11.2 kA·m-1 revealed a achievable plateau surface temperature of Tsurf = 57±1 °C for NC-mNP-OCL recorded by an infrared video camera. An effective heat generation constant (̅P) can be derived from a multi-scale model for the heat generation, which is proportional to the rate of heat generation per unit volume of the sample. NC-mNP-OCL with homogeneously dispersed mNP-OCLs exhibited a ̅P value of 1.04±0.01 K·s- 1 at Hhigh, while at Hreset = 30.0 kA·m-1 a Tsurf of 88±1 °C (where all OPDL related crystallite are molten) and a ̅P value of 1.93±0.02 K·s-1 was obtained indicating a high magnetic heating capability of the composite.
The free-standing magnetically-controlled reversible shape-memory effect (mrSME) was explored with originally straight nanocomposite samples programmed by bending to an angle of 180°. By switching the magnetic field on and off the composite sample was allowed to repetitively heat to 60 °C and cool to the ambient temperature. A pronounced mrSME, characterized by changes in bending angle of Δϐrev = 20±3° could be obtained for a composite sample programmed by bending when a magnetic field strength of Hhigh = 11.2 kA·m-1 was applied in a multi-cyclic magnetic bending experiment with 600 heating-cooling cycles it could be shown that the actuation performance did not change with increasing number of test cycles, demonstrating the accuracy and reproducibility of this soft actuator. The degree of actuation as well as the kinetics of the shape changes during heating could be tuned by variation of the magnetic filed strength between Hlow and Hhigh or the magnetic field exposure time. When Hreset = 30.0 kA·m-1 was applied the programmed geometry was erased and the composite sample returned to it´s originally straight shape. The reprogrammability of the nanocomposite actuators was demonstrated by one and the same test specimen first exhibiting reversible angle changes when programmed by bending, secondly reprogrammed to a concertina, which expands upon inductive heating and contracts during cooling and finally reprogrammed to a clip like shape, which closes during cooling and opens when Hhigh was applied. In a next step the applicability of the presented remote controllable shape-memory polymer actuators was demonstrated by repetitive opening and closing of a multiring device prepared from NC-mNP-OCL, which repetitively opens and closes when a alternating magnetic field (Hhigh = 11.2 kA·m-1) was switched on and off.
For investigation of the micro- and nanostructural changes related to the actuation of the developed nanocomposite, AFM and WAXS experiments were conducted with programmed nanocomposite samples under cyclic heating and cooling between 25 °C and 60 °C. In AFM experiments the change in the distance (D) between representative droplet-like structures related to the OPDL geometry determining domains was used to calculate the reversible change in D. Here Drev = 3.5±1% was found for NC-mNP-OCL which was in good agreement with the results of the magneto-mechanical actuation experiments. Finally, the analysis of azimuthal (radial) WAXS scattering profiles could support the oriented crystallization of the OCL actuation domains at 25 °C.
In conclusion, the results of this work successfully demonstrated that shape-memory polymer nanocomposites, containing mNPs as magneto-sensitive multifunctional netpoints in a covalently crosslinked multiphase polymer matrix, exhibit magnetically (remotely) controlled actuations upon repetitive exposure to an alternating magnetic field. Furthermore, the (shape) memory of such a nanocomposite can be erased by exposing it to temperatures above the melting temperature of the geometry forming domains, which allows a reprogramming of the actuator. These findings would be relevant for designing novel reprogrammable remotely controllable soft polymeric actuators.
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.
To reach its climate targets, the European Union has to implement a major sustainability transition in the coming decades. While the socio-technical change required for this transition is well discussed in the academic literature, the economics that go along with it are often reduced to a cost-benefit perspective of climate policy measures. By investigating climate change mitigation as a coordination problem, this thesis offers a novel perspective: It integrates the economic and the socio-technical dimension and thus allows to better understand the opportunities of a sustainability transition in Europe.
First, a game theoretic framework is developed to illustrate coordination on green or brown investment from an agent perspective. A model based on the coordination game "stag hunt" is used to discuss the influence of narratives and signals for green investment as a means to coordinate expectations towards green growth. Public and private green investment impulses – triggered by credible climate policy measures and targets – serve as an example for a green growth perspective for Europe in line with a sustainability transition. This perspective also embodies a critical view on classical analyses of climate policy measures.
Secondly, this analysis is enriched with empirical results derived from stakeholder involvement. In interviews and with a survey among European insurance companies, coordination mechanisms such as market and policy signals are identified and evaluated by their impact on investment strategies for green infrastructure. The latter, here defined as renewable energy, electricity distribution and transmission as well as energy efficiency improvements, is considered a central element of the transition to a low-carbon society.
Thirdly, this thesis identifies and analyzes major criticisms raised towards stakeholder involvement in sustainability science. On a conceptual level, different ways of conducting such qualitative research are classified. This conceptualization is then evaluated by scientists, thereby generating empirical evidence on ideals and practices of stakeholder involvement in sustainability science.
Through the combination of theoretical and empirical research on coordination problems, this thesis offers several contributions: On the one hand, it outlines an approach that allows to assess the economic opportunities of sustainability transitions. This is helpful for policy makers in Europe that are striving to implement climate policy measures addressing the targets of the Paris Agreement as well as to encourage a shift of investments towards green infrastructure. On the other hand, this thesis enhances the stabilization of the theoretical foundations in sustainability science. Therefore, it can aid researchers who involve stakeholders when studying sustainability transitions.
Uncertainty is an essential part of atmospheric processes and thus inherent to weather forecasts. Nevertheless, weather forecasts and warnings are still predominately issued as deterministic (yes or no) forecasts, although research suggests that providing weather forecast users with additional information about the forecast uncertainty can enhance the preparation of mitigation measures. Communicating forecast uncertainty would allow for a provision of information on possible future events at an earlier time. The desired benefit is to enable the users to start with preparatory protective action at an earlier stage of time based on the their own risk assessment and decision threshold. But not all users have the same threshold for taking action. In the course of the project WEXICOM (‘Wetterwarnungen: Von der Extremereignis-Information zu Kommunikation und Handlung’) funded by the Deutscher Wetterdienst (DWD), three studies were conducted between the years 2012 and 2016 to reveal how weather forecasts and warnings are reflected in weather-related decision-making. The studies asked which factors influence the perception of forecasts and the decision to take protective action and how forecast users make sense of probabilistic information and the additional lead time. In a first exploratory study conducted in 2012, members of emergency services in Germany were asked questions about how weather warnings are communicated to professional endusers in the emergency community and how the warnings are converted into mitigation measures. A large number of open questions were selected to identify new topics of interest. The questions covered topics like users’ confidence in forecasts, their understanding of probabilistic information as well as their lead time and decision thresholds to start with preparatory mitigation measures. Results show that emergency service personnel generally have a good sense of uncertainty inherent in weather forecasts. Although no single probability threshold could be identified for organisations to start with preparatory mitigation measures, it became clear that emergency services tend to avoid forecasts based on low probabilities as a basis for their decisions. Based on this findings, a second study conducted with residents of Berlin in 2014 further investigated the question of decision thresholds. The survey questions related to the topics of the perception of and prior experience with severe weather, trustworthiness of forecasters and confidence in weather forecasts, and socio-demographic and social-economic characteristics. Within the questionnaire a scenario was created to determine individual decision thresholds and see whether subgroups of the sample lead to different thresholds. The results show that people’s willingness to act tends to be higher and decision thresholds tend to be lower if the expected weather event is more severe or the property at risk is of higher value. Several influencing factors of risk perception have significant effects such as education, housing status and ability to act, whereas socio-demographic determinants alone are often not sufficient to fully grasp risk perception and protection behaviour. Parallel to the quantitative studies, an interview study was conducted with 27 members of German civil protection between 2012 and 2016. The results show that the latest developments in (numerical) weather forecasting do not necessarily fit the current practice of German emergency services. These practices are mostly carried out on alarms and ground truth in a reactive manner rather than on anticipation based on prognosis or forecasts. As the potential consequences rather than the event characteristics determine protective action, the findings support the call and need for impact-based warnings. Forecasters will rely on impact data and need to learn the users’ understanding of impact. Therefore, it is recommended to enhance weather communication not only by improving computer models and observation tools, but also by focusing on the aspects of communication and collaboration. Using information about uncertainty demands awareness about and acceptance of the limits of knowledge, hence, the capabilities of the forecaster to anticipate future developments of the atmosphere and the capabilities of the user to make sense of this information.
Light-driven diffusioosmosis
(2018)
The emergence of microfluidics created the need for precise and remote control of micron-sized objects. I demonstrate how light-sensitive motion can be induced at the micrometer scale by a simple addition of a photosensitive surfactant, which makes it possible to trigger hydrophobicity with light. With point-like laser irradiation, radial inward and outward hydrodynamic surface flows are remotely switched on and off. In this way, ensembles of microparticles can be moved toward or away from the irradiation center. Particle motion is analyzed according to varying parameters, such as surfactant and salt concentration, illumination condition, surface hydrophobicity, and surface structure.
The physical origin of this process is the so-called light-driven diffusioosmosis (LDDO), a phenomenon that was discovered in the framework of this thesis and is described experimentally and theoretically in this work. To give a brief explanation, a focused light irradiation induces a local photoisomerization that creates a concentration gradient at the solid-liquid interface. To compensate for the change in osmotic pressure near the surface, a hydrodynamic flow along the surface is generated. Surface-surfactant interaction largely governs LDDO. It is shown that surfactant adsorption depends on the isomerization state of the surfactant. Photoisomerization, therefore, triggers a surfactant attachment or detachment from the surface. This change is considered to be one of the reasons for the formation of LDDO flow.
These flows are introduced not only by a focused laser source but also by global irradiation. Porous particles show reversible repulsive and attractive interactions when dispersed in the solution of photosensitive surfactant. Repulsion and attraction is controlled by the irradiation wavelength. Illumination with red light leads to formation of aggregates, while illumination with blue light leads to the formation of a well-separated grid with equal interparticle distances, between 2µm and 80µm, depending on the particle surface density. These long-range interactions are considered to be a result of an increase or decrease of surfactant concentration around each particle, depending on the irradiation wavelength. Surfactant molecules adsorb inside the pores of the particles. A light-induced photoisomerization changes adsorption to the pores and drives surfactant molecules to the outside. The concentration gradients generate symmetric flows around each single particle resulting in local LDDO. With a break of the symmetry (i.e., by closing one side of the particle with a metal cap), one can achieve active self-propelled particle motion.