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It has been known for several years that under certain conditions electrons can be confined within thin layers even if these layers consist of metal and are supported by a metal substrate. In photoelectron spectra, these layers show characteristic discrete energy levels and it has turned out that these lead to large effects like the oscillatory magnetic coupling technically exploited in modern hard disk reading heads. The current work asks in how far the concepts underlying quantization in two-dimensional films can be transferred to lower dimensionality. This problem is approached by a stepwise transition from two-dimensional layers to one-dimensional nanostructures. On the one hand, these nanostructures are represented by terraces on atomically stepped surfaces, on the other hand by atom chains which are deposited onto these terraces up to complete coverage by atomically thin nanostripes. Furthermore, self organization effects are used in order to arrive at perfectly one-dimensional atomic arrangements at surfaces. Angle-resolved photoemission is particularly suited as method of investigation because is reveals the behavior of the electrons in these nanostructures in dependence of the spacial direction which distinguishes it from, e. g., scanning tunneling microscopy. With this method intense and at times surprisingly large effects of one-dimensional quantization are observed for various exemplary systems, partly for the first time. The essential role of bandgaps in the substrate known from two-dimensional systems is confirmed for nanostructures. In addition, we reveal an ambiguity without precedent in two-dimensional layers between spacial confinement of electrons on the one side and superlattice effects on the other side as well as between effects caused by the sample and by the measurement process. The latter effects are huge and can dominate the photoelectron spectra. Finally, the effects of reduced dimensionality are studied in particular for the d electrons of manganese which are additionally affected by strong correlation effects. Surprising results are also obtained here. ---------------------------- Die Links zur jeweiligen Source der im Appendix beigefügten Veröffentlichungen befinden sich auf Seite 83 des Volltextes.
In a classical context, synchronization means adjustment of rhythms of self-sustained periodic oscillators due to their weak interaction. The history of synchronization goes back to the 17th century when the famous Dutch scientist Christiaan Huygens reported on his observation of synchronization of pendulum clocks: when two such clocks were put on a common support, their pendula moved in a perfect agreement. In rigorous terms, it means that due to coupling the clocks started to oscillate with identical frequencies and tightly related phases. Being, probably, the oldest scientifically studied nonlinear effect, synchronization was understood only in 1920-ies when E. V. Appleton and B. Van der Pol systematically - theoretically and experimentally - studied synchronization of triode generators. Since that the theory was well developed and found many applications. Nowadays it is well-known that certain systems, even rather simple ones, can exhibit chaotic behaviour. It means that their rhythms are irregular, and cannot be characterized only by one frequency. However, as is shown in the Habilitation work, one can extend the notion of phase for systems of this class as well and observe their synchronization, i.e., agreement of their (still irregular!) rhythms: due to very weak interaction there appear relations between the phases and average frequencies. This effect, called phase synchronization, was later confirmed in laboratory experiments of other scientific groups. Understanding of synchronization of irregular oscillators allowed us to address important problem of data analysis: how to reveal weak interaction between the systems if we cannot influence them, but can only passively observe, measuring some signals. This situation is very often encountered in biology, where synchronization phenomena appear on every level - from cells to macroscopic physiological systems; in normal states as well as in severe pathologies. With our methods we found that cardiovascular and respiratory systems in humans can adjust their rhythms; the strength of their interaction increases with maturation. Next, we used our algorithms to analyse brain activity of Parkinsonian patients. The results of this collaborative work with neuroscientists show that different brain areas synchronize just before the onset of pathological tremor. Morevoever, we succeeded in localization of brain areas responsible for tremor generation.
Over millennia, droughts could not be understood or defined but rather were associated with mystical connotations. To understand this natural hazards, we first needed to understand the laws of physics and then develop plausible explanations of inner workings of the hydrological cycle. Consequently, modeling and predicting droughts was out of the scope of mankind until the end of the last century. In recent studies, it is estimated that this natural hazard has caused billions of dollars in losses since 1900 and that droughts have affected 2.2 billion people worldwide between 1950 and 2014.
For these reasons, droughts have been identified by the IPCC as the trigger of a web of impacts across many sectors leading to land degradation, migration and substantial socio-economic costs. This thesis summarizes a decade of research carried out at the Helmholtz Centre for Environmental Research on the subject of drought monitoring, modeling, and forecasting, from local to continental scales. The overarching objectives of this study, systematically addressed in the twelve previous chapters, are: 1) Create the capability to seamless monitor and predict water fluxes at various spatial resolutions and temporal scales varying from days to centuries; 2) Develop and test a modeling chain for monitoring, forecasting and predicting drought events and related characteristics at national and continental scales; and 3) Develop drought indices and impact indicators that are useful for end-users. Key outputs of this study are: the development of the open source model mHM, the German Drought Monitor System, the proof of concept for an European multi-model for improving water managent from local to continental scales, and the prototype of a crop-yield drought impact model for Germany.
Carbon nitride semiconductors: properties and application as photocatalysts in organic synthesis
(2023)
Graphitic carbon nitrides (g-CNs) are represented by melon-type g-CN, poly(heptazine imides) (PHIs), triazine-based g-CN and poly(triazine imide) with intercalated LiCl (PTI/Li+Cl‒). These materials are composed of sp2-hybridized carbon and nitrogen atoms; C:N ratio is close to 3:4; the building unit is 1,3,5-triazine or tri-s-triazine; the building units are interconnected covalently via sp2-hybridized nitrogen atoms or NH-moieties; the layers are assembled into a stack via weak van der Waals forces as in graphite. Due to medium band gap (~2.7 eV) g-CNs, such as melon-type g-CN and PHIs, are excited by photons with wavelength ≤ 460 nm. Since 2009 g-CNs have been actively studied as photocatalysts in evolution of hydrogen and oxygen – two half-reactions of full water splitting, by employing corresponding sacrificial agents. At the same time application of g-CNs as photocatalysts in organic synthesis has been remaining limited to few reactions only. Cumulative Habilitation summarizes research work conducted by the group ‘Innovative Heterogeneous Photocatalysis’ between 2017-2023 in the field of carbon nitride organic photocatalysis, which is led by Dr. Oleksandr Savatieiev.
g-CN photocatalysts activate molecules, i.e. generate their more reactive open-shell intermediates, via three modes: i) Photoinduced electron transfer (PET); ii) Excited state proton-coupled electron transfer (ES-PCET) or direct hydrogen atom transfer (dHAT); iii) Energy transfer (EnT). The scope of reactions that proceed via oxidative PET, i.e. one-electron oxidation of a substrate to the corresponding radical cation, are represented by synthesis of sulfonylchlorides from S-acetylthiophenols. The scope of reactions that proceed via reductive PET, i.e. one-electron reduction of a substrate to the corresponding radical anion, are represented by synthesis of γ,γ-dichloroketones from the enones and chloroform.
Due to abundance of sp2-hybridized nitrogen atoms in the structure of g-CN materials, they are able to cleave X-H bonds in organic molecules and store temporary hydrogen atom. ES-PCET or dHAT mode of organic molecules activation to the corresponding radicals is implemented for substrates featuring relatively acidic X-H bonds and those that are characterized by low bond dissociation energy, such as C-H bond next to the heteroelements. On the other hand, reductively quenched g-CN carrying hydrogen atom reduces a carbonyl compound to the ketyl radical via PCET that is thermodynamically more favorable pathway compared to the electron transfer. The scope of these reactions is represented by cyclodimerization of α,β-unsaturated ketones to cyclopentanoles.
g-CN excited state demonstrates complex dynamics with the initial formation of singlet excited state, which upon intersystem crossing produces triplet excited state that is characterized by the lifetime > 2 μs. Due to long lifetime, g-CN activate organic molecules via EnT. For example, g-CN sensitizes singlet oxygen, which is the key intermediate in the dehydrogenation of aldoximes to nitrileoxides. The transient nitrileoxide undergoes [3+2]-cycloaddition to nitriles and gives oxadiazoles-1,2,4.
PET, ES-PCET and EnT are fundamental phenomena that are applied beyond organic photocatalysis. Hybrid composite is formed by combining conductive polymers, such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) with potassium poly(heptazine imide) (K-PHI). Upon PET, K-PHI modulated population of polarons and therefore conductivity of PEDOT:PSS. The initial state of PEDOT:PSS is recovered upon material exposure to O2. K-PHI:PEDOT:PSS may be applied in O2 sensing.
In the presence of electron donors, such as tertiary amines and alcohols, and irradiation with light, K-PHI undergoes photocharging – the g-CN material accumulates electrons and charge-compensating cations. Such photocharged state is stable under anaerobic conditions for weeks, but at the same time it is a strong reductant. This feature allows decoupling in time light harvesting and energy storage in the form of electron-proton couples from utilization in organic synthesis. The photocharged state of K-PHI reduces nitrobenzene to aniline, and enables dimerization of α,β-unsaturated ketones to hexadienones in dark.
The anatomically modern human Homo sapiens sapiens is distinguished by a high adaptability in physiology, physique and behaviour in short term changing environmental conditions. Since our environmental factors are constantly changing because of anthropogenic influences, the question arises as to how far we have an impact on the human phenotype in the very sensitive growth phase in children and adolescents. Growth and development of all children and adolescents follow a universal and typical pattern. This pattern has evolved as the result of trade-offs in the 6-7 million years of human evolution. This typically human growth pattern differs from that of other long-living social primate species. It can be divided into different biological age stages, with specific biological, cognitive and socio-cultural signs. Phenotypic plasticity is the ability of an organism to react to an internal or external environmental input with a change in the form, state, and movement rate of activity (West-Eberhard 2003). The plasticity becomes visible and measurable particularly when, in addition to the normal variability of the phenotypic characteristics within a population, the manifestation of this plasticity changes within a relatively short time. The focus of the present work is the comparison of age-specific dimensional changes. The basic of the presented studies are more than 75,000 anthropometric data-sets of children and adolescence from 1980 up today and historical data of height available in scientific literature. Due to reduced daily physical activity, today's 6-18 year-olds have lower values of pelvic and elbow breadths. The observed increase in body height can be explained by hierarchies in social networks of human societies, contrary to earlier explanations (influence of nutrition, good living conditions and genetics). A shift towards a more feminine fat distribution pattern in boys and girls is parallel to the increase in chemicals in our environment that can affect the hormone system. Changing environmental conditions can have selective effects over generations so that that genotype becomes increasingly prevalent whose individuals have a higher progeny rate than other individuals in this population. Those then form the phenotype which allows optimum adaptation to the changes of the environmental conditions. Due to the slow patterns of succession and the low progeny rate (Hawkes et al. 1998), fast visible in the phenotype due to changes in the genotype of a population are unlikely to occur in the case of Homo sapiens sapiens within short time. In the data sets on which the presented investigations are based, such changes appear virtually impossible. The study periods cover 5-30 to max.100 years (based on data from the body height from historical data sets).
In this work, the basic principles of self-organization of diblock copolymers having the in¬herent property of selective or specific non-covalent binding were examined. By the introduction of electrostatic, dipole–dipole, or hydrogen bonding interactions, it was hoped to add complexity to the self-assembled mesostructures and to extend the level of ordering from the nanometer to a larger length scale. This work may be seen in the framework of biomimetics, as it combines features of synthetic polymer and colloid chemistry with basic concepts of structure formation applying in supramolecular and biological systems. The copolymer systems under study were (i) block ionomers, (ii) block copolymers with acetoacetoxy chelating units, and (iii) polypeptide block copolymers.
The habilitation thesis presented here includes results from several studies dealing with fluid-rock interactions and rock deformation processes in active fault zones. The focus in all of these studies is on the influence of clay minerals on the geochemical and the hydro-mechanical behavior of the fault rocks. The research was conducted on rock cores and cuttings from four scientific drilling projects at the San Andreas Fault (USA), the Nankai Trough subduction zone and the Japan Trench subduction zone (Japan), as well as the Alpine Fault in New Zealand. These ICDP (International Continental Scientific Drilling Program) and IODP (International Ocean Discovery Program) funded projects were all conducted with the aim to monitor and better understand earthquakes.
Chapter 1 contains a short introduction to the topic with basic principles and objectives regarding the research approach. Chapter 2 describes the state of the art in clay mineral and fault zone science, gives a short description of the individual drilling projects and their locations on which the research was based, and summarizes the most important analytical methods used. Chapter 3 comprises ten peer-reviewed publications that are connected thematically and methodologically. The papers were published in the years 2006-2015, and additional related publications including myself as co-author are given in the literature list. The ten publications address different questions concerning the formation of clay minerals and processes of fluid-rock interaction in active fault zones. Six papers contain results from the SAFOD drilling project, USA (San Andreas Fault Observatory at Depth), with the main focus on fluid-rock interaction processes in fault rocks and the formation and location of clay minerals. Three publications report on research from the NanTroSEIZE drilling project (Nankai Trough Seismogenic Zone Experiment) and the JFAST drilling project (Japan Trench Fast Drilling Project). Both projects are situated in Japan. Here, the swelling behavior of smectite clay minerals in relation to changing environmental conditions (e.g. temperature and/or humidity) was investigated. The last publication included here concerns a study from the DFDP project (Deep Fault Drilling Project) in New Zealand, where I investigated the deformation of clay minerals on the context of the hydro-mechanical behavior of the fault zone rocks. I was first author in nine of the publications and in charge of the project preparation, measurements and data analyses, and the completion of the manuscript. As co-author on the other publication I was responsible for electronmicroscopy analyses (SEM and TEM) and their interpretation.
The key results from the publications in Chapter 3 are discussed in Chapter 4 with additional considerations from more recent papers. Following the major theses in Chapter 5, Chapter 6 highlights a future research project in clay mineralogy research at the GFZ. An appendix includes more detailed descriptions of the laboratory equipment and lists of all publications, conference contributions and teaching courses and modules.
In the present thesis, self-assembly of hydrophilic polymers, reinforced hydrogels and inorganic/polymer hybrids were examined. The thesis describes an avenue from polymer synthesis via various methods over polymer self-assembly to the formation of polymer materials that have promising properties for future applications.
Hydrophilic polymers were utilized to form multi-phase systems, water-in-water emulsions and self-assembled structures, e.g. particles/aggregates or hollow structures from completely water-soluble building blocks. The structuring of aqueous environments by hydrophilic homo and block copolymers was further utilized in the formation of supramolecular hydrogels with compartments or specific thermal behavior. Furthermore, inorganic graphitic carbon nitride (g-CN) was utilized as photoinitiator for hydrogel formation and as reinforcer for hydrogels. As such, hydrogels with remarkable mechanical properties were synthesized, e.g. high compressibility, high storage modulus or lubricity. In addition, g-CN was combined with polymers for a broad range of materials, e.g. coatings, films or latex, that could be utilized in photocatalytic applications. Another inorganic material class was combined with polymers in the present thesis as well, namely metal-organic frameworks (MOFs). It was shown that the pore structure of MOFs enables improved control over tacticity and achievement of high molar masses. Furthermore, MOF-based polymerization catalysis was introduced with improved control for coordinating monomers, catalyst recyclability and decreased metal contamination in the product. Finally, the effect of external influence on MOF morphology was studied, e.g. via solvent or polymer additives, which allowed the formation of various MOF structures.
Overall, advances in several areas of polymer science are presented in here. A major topic of the thesis was hydrophilic polymers and hydrogels that currently constitute significant materials in the polymer field due to promising future applications in biomedicine. Moreover, the combination of polymers with materials from other areas of research, i.e. g-CN and MOFs, provided various new materials with remarkable properties also of interest for applications in the future, e.g. coatings, particle structures and catalysis.
Rivers have always flooded their floodplains. Over 2.5 billion people worldwide have been affected by flooding in recent decades. The economic damage is also considerable, averaging 100 billion US dollars per year. There is no doubt that damage and other negative effects of floods can be avoided. However, this has a price: financially and politically. Costs and benefits can be estimated through risk assessments. Questions about the location and frequency of floods, about the objects that could be affected and their vulnerability are of importance for flood risk managers, insurance companies and politicians. Thus, both variables and factors from the fields of hydrology and sociol-economics play a role with multi-layered connections. One example are dikes along a river, which on the one hand contain floods, but on the other hand, by narrowing the natural floodplains, accelerate the flood discharge and increase the danger of flooding for the residents downstream. Such larger connections must be included in the assessment of flood risk. However, in current procedures this is accompanied by simplifying assumptions. Risk assessments are therefore fuzzy and associated with uncertainties.
This thesis investigates the benefits and possibilities of new data sources for improving flood risk assessment. New methods and models are developed, which take the mentioned interrelations better into account and also quantify the existing uncertainties of the model results, and thus enable statements about the reliability of risk estimates. For this purpose, data on flood events from various sources are collected and evaluated. This includes precipitation and flow records at measuring stations as well as for instance images from social media, which can help to delineate the flooded areas and estimate flood damage with location information. Machine learning methods have been successfully used to recognize and understand correlations between floods and impacts from a wide range of data and to develop improved models.
Risk models help to develop and evaluate strategies to reduce flood risk. These tools also provide advanced insights into the interplay of various factors and on the expected consequences of flooding. This work shows progress in terms of an improved assessment of flood risks by using diverse data from different sources with innovative methods as well as by the further development of models. Flood risk is variable due to economic and climatic changes, and other drivers of risk. In order to keep the knowledge about flood risks up-to-date, robust, efficient and adaptable methods as proposed in this thesis are of increasing importance.
The behaviour of an adhering cell is strongly influenced by the chemical, topographical and mechanical properties of the surface it attaches to. During recent years, it has been found experimentally that adhering cells actively sense the elastic properties of their environment by pulling on it through numerous sites of adhesion. The resulting build-up of force at sites of adhesion depends on the elastic properties of the environment and is converted into corresponding biochemical signals, which can trigger cellular programmes like growth, differentiation, apoptosis, and migration. In general, force is an important regulator of biological systems, for example in hearing and touch, in wound healing, and in rolling adhesion of leukocytes on vessel walls. In the habilitation thesis by Ulrich Schwarz, several theoretical projects are presented which address the role of forces and elasticity in cell adhesion. (1) A new method has been developed for calculating cellular forces exerted at sites of focal adhesion on micro-patterned elastic substrates. The main result is that cell-matrix contacts function as mechanosensors, converting internal force into protein aggregation. (2) A one-step master equation for the stochastic dynamics of adhesion clusters as a function of cluster size, rebinding rate and force has been solved both analytically and numerically. Moreover this model has been applied to the regulation of cell-matrix contacts, to dynamic force spectroscopy, and to rolling adhesion. (3) Using linear elasticity theory and the concept of force dipoles, a model has been introduced and solved which predicts the positioning and orientation of mechanically active cells in soft material, in good agreement with experimental observations for fibroblasts on elastic substrates and in collagen gels.
Fabricating electronic devices from natural, renewable resources has been a common goal in engineering and materials science for many years. In this regard, carbon is of special significance due to its biological compatibility. In the laboratory, carbonized materials and their composites have been proven as promising solutions for a range of future applications in electronics, optoelectronics, or catalytic systems. On the industrial scale, however, their application is inhibited by tedious and expensive preparation processes and a lack of control over the processing and material parameters. Therefore, we are exploring new concepts for the direct utilization of functional carbonized materials in electronic applications. In particular, laser-induced carbonization (carbon laser-patterning (CLaP)) is emerging as a new tool for the precise and selective synthesis of functional carbon-based materials for flexible on-chip applications.
We developed an integrated approach for on-the-spot laser-induced synthesis of flexible, carbonized films with specific functionalities. To this end, we design versatile precursor inks made from naturally abundant starting compounds and reactants to cast films which are carbonized with an infrared laser to obtain functional patterns of conductive porous carbon networks. In our studies we obtained deep mechanistic insights into the formation process and the microstructure of laser-patterned carbons (LP-C). We shed light on the kinetic reaction mechanism based on the interplay between the precursor properties and the reaction conditions. Furthermore, we investigated the use of porogens, additives, and reactants to provide a toolbox for the chemical and physical fine-tuning of the electronic and surface properties and the targeted integration of functional sites into the carbon network. Based on this knowledge, we developed prototype resistive chemical and mechanical sensors. In further studies, we show the applicability of LP-C as electrode materials in electrocatalytic and charge-storage applications.
To put our findings into a common perspective, our results are embedded into the context of general carbonization strategies, fundamentals of laser-induced materials processing, and a broad literature review on state-of-the-art laser-carbonization, in the general part.
The geochemical composition of oceanic basalts provides us with a window into the distribution of geochemical elements within the Earth’s mantle in space and time. In conjunction with a throughout knowledge on how the different elements behave e.g. during melt formation and evolution or on their partition behaviour between e.g. minerals and melts this information has been transformed into various models on how oceanic crust is formed along plume influenced or normal mid-ocean ridge segments, how oceanic crust evolves in response to seawater, on subduction recycling of oceanic crust and so forth. The work presented in this habilitation was aimed at refining existing models, putting further constraints on some of the major open questions in this field of research while at the same time trying to increase our knowledge on the behaviour of noble gases as a tracer for melt formation and evolution processes. In the line of this work the author and her co-workers were able to answer one of the major questions concerning the formation of oceanic crust along plume-influenced ridges – in which physical state does the plume material enter the ridge? Based on submarine volcanic glass He, Ne and Ar data, the author and her co-workers have shown that the interaction of mantle plumes with mid-ocean ridges occurs in the physical form of melts. In addition, the author and her co-workers have also put further constraints on one of the major questions concerning the formation of oceanic crust along normal mid-ocean ridges – namely how is the mid-ocean ridge system effectively cooled to form the lower oceanic crust? Based on Ne and Ar data in combination with Cl/K ratios of basaltic glass from the Mid-Atlantic ridge and estimates of crystallisation pressures they have shown, that seawater penetration reaches lower crustal levels close to the Moho, indicating that hydrothermal circulation might be an effective cooling mechanism even for the deep parts of the oceanic crust. Considering subduction recycling, the heterogeneity of the Earth’s mantle and mantle dynamic processes the key question is on which temporal and spatial scales is the Earth’s mantle geochemically heterogeneous? In the line of this work the author along with her co-workers have shown based on Cl/K ratios in conjunction with the Sr, Nd, and Pb isotopes of the OIBs representing the type localities for the different mantle endmembers that the quantity of Cl recycled into the mantle via subduction is not uniform and that neither the HIMU nor the EM1 and EM2 mantle components can be considered as distinct mantle endmembers. In addition, we have shown, based on He, Ne and Ar isotope and trace-element data from the Foundation hotspot that the near ridge seamounts of the Foundation seamount chain formed by the Foundation hotspot erupt lavas with a trace-element signature clearly characteristic of oceanic gabbro which indicates the existence of recycled, virtually unchanged lower oceanic crust in the plume source. This is a clear sign of the inefficiency of the stirring mechanism existing at mantle depth. Similar features are seen in other near-axis hotspot magmas around the world. Based on He, Sr, Nd, Pb and O isotopes and trace elements in primitive mafic dykes from the Etendeka flood basalts, NW Namibia the author along with her co-workers have shown that deep, less degassed mantle material carried up by a mantle plume contributed significantly to the flood basalt magmatism. The Etendeka flood basalts are part of the South Atlantic LIP, which is associated with the breakup of Gondwana, the formation of the Paraná-Etendeka flood basalts and the Walvis Ridge - Tristan da Cunha hotspot track. Thus reinforcing the lately often-challenged concept of mantle plumes and the role of mantle plumes in the formation of large igneous provinces. Studying the behaviour of noble gases during melt formation and evolution the author along with her co-workers has shown that He can be considerable more susceptible to changes during melt formation and evolution resulting not only in a complete decoupling of He isotopes from e.g. Ne or Pb isotopes but also in a complete loss of the primary mantle isotope signal. They have also shown that this decoupling occurs mainly during the melt formation processes requiring He to be more compatible during mantle melting than Ne. In addition, the author along with her co workers were able to show that incorporation of atmospheric noble gases into igneous rocks is in general a two-step process: (1) magma contamination by assimilation of altered oceanic crust results in the entrainment of air-equilibrated seawater noble gases; (2) atmospheric noble gases are adsorbed onto grain surfaces during sample preparation. This implies, considering the ubiquitous presence of the contamination signal, that magma contamination by assimilation of a seawater-sourced component is an integral part of mid-ocean ridge basalt evolution.
This thesis deals with different aspects of flood risk in Germany. In twelve papers new scientific findings about flood hazards, factors that influence flood losses as well as effective private precautionary measures are presented. The seasonal distribution of flooding is shown for the whole of Germany. Furthermore, possible impacts of climate change on discharge and flood frequencies are estimated for the catchment of the river Rhine. Moreover, it is simulated at reaches of the Lower Rhine, which effects may result from levee breaches. Flood losses are the focus of the second part of the thesis: After the flood in August 2002 approximately 1700 households were interviewed by telephone. By this, it was possible to quantify the influence of different factors such as flood duration or the contamination of the flood water with oil on the extent of financial flood damage. On this basis, a new model was derived, by which flood losses can be calculated on a large scale. On the other hand, it was possible to derive recommendations for the improvement of private precaution. For example, the analysis revealed that insured households were compensated more quickly and to a better degree than uninsured. It became also clear that different groups like tenants and homeowners have different capabilities of performing precaution. This is to be considered in future risk communication. In 2005 and 2006, the rivers Elbe and Danube were again affected by flooding. A renewed pool among households and public authorities enabled us to investigate the improvement of flood risk management and the precaution in the City of Dresden. Several methods and finding of this thesis are applicable for water resources management issues and contribute to an improvement of flood risk analysis and management in Germany.
Hydrothermal carbonisation
(2013)
The world’s appetite for energy is producing growing quantities of CO2, a pollutant that contributes to the warming of the planet and which currently cannot be removed or stored in any significant way. Other natural reserves are also being devoured at alarming rates and current assessments suggest that we will need to identify alternative sources in the near future. With the aid of materials chemistry it should be possible to create a world in which energy use needs not be limited and where usable energy can be produced and stored wherever it is needed, where we can minimize and remediate emissions as new consumer products are created, whilst healing the planet and preventing further disruptive and harmful depletion of valuable mineral assets. In achieving these aims, the creation of new and very importantly greener industries and new sustainable pathways are crucial. In all of the aforementioned applications, new materials based on carbon, ideally produced via inexpensive, low energy consumption methods, using renewable resources as precursors, with flexible morphologies, pore structures and functionalities, are increasingly viewed as ideal candidates to fulfill these goals. The resulting materials should be a feasible solution for the efficient storage of energy and gases. At the end of life, such materials ideally must act to improve soil quality and to act as potential CO2 storage sinks. This is exactly the subject of this habilitation thesis: an alternative technology to produce carbon materials from biomass in water using low carbonisation temperatures and self-generated pressures. This technology is called hydrothermal carbonisation. It has been developed during the past five years by a group of young and talented researchers working under the supervision of Dr. Titirici at the Max-Planck Institute of Colloids and Interfaces and it is now a well-recognised methodology to produce carbon materials with important application in our daily lives. These applications include electrodes for portable electronic devices, filters for water purification, catalysts for the production of important chemicals as well as drug delivery systems and sensors.
The Sun is surrounded by a 10^6 K hot atmosphere, the corona. The corona and the solar wind are fully ionized, and therefore in the plasma state. Magnetic fields play an important role in a plasma, since they bind electrically charged particles to their field lines. EUV spectroscopes, like the SUMER instrument on-board the SOHO spacecraft, reveal a preferred heating of coronal ions and strong temperature anisotropies. Velocity distributions of electrons can be measured directly in the solar wind, e.g. with the 3DPlasma instrument on-board the WIND satellite. They show a thermal core, an anisotropic suprathermal halo, and an anti-solar, magnetic-field-aligned, beam or "strahl". For an understanding of the physical processes in the corona, an adequate description of the plasma is needed. Magnetohydrodynamics (MHD) treats the plasma simply as an electrically conductive fluid. Multi-fluid models consider e.g. protons and electrons as separate fluids. They enable a description of many macroscopic plasma processes. However, fluid models are based on the assumption of a plasma near thermodynamic equilibrium. But the solar corona is far away from this. Furthermore, fluid models cannot describe processes like the interaction with electromagnetic waves on a microscopic scale. Kinetic models, which are based on particle velocity distributions, do not show these limitations, and are therefore well-suited for an explanation of the observations listed above. For the simplest kinetic models, the mirror force in the interplanetary magnetic field focuses solar wind electrons into an extremely narrow beam, which is contradicted by observations. Therefore, a scattering mechanism must exist that counteracts the mirror force. In this thesis, a kinetic model for electrons in the solar corona and wind is presented that provides electron scattering by resonant interaction with whistler waves. The kinetic model reproduces the observed components of solar wind electron distributions, i.e. core, halo, and a "strahl" with finite width. But the model is not only applicable on the quiet Sun. The propagation of energetic electrons from a solar flare is studied, and it is found that scattering in the direction of propagation and energy diffusion influence the arrival times of flare electrons at Earth approximately to the same degree. In the corona, the interaction of electrons with whistler waves does not only lead to scattering, but also to the formation of a suprathermal halo, as it is observed in interplanetary space. This effect is studied both for the solar wind as well as the closed volume of a coronal magnetic loop. The result is of fundamental importance for solar-stellar relations. The quiet solar corona always produces suprathermal electrons. This process is closely related to coronal heating, and can therefore be expected in any hot stellar corona. In the second part of this thesis it is detailed how to calculate growth or damping rates of plasma waves from electron velocity distributions. The emission and propagation of electron cyclotron waves in the quiet solar corona, and that of whistler waves during solar flares, is studied. The latter can be observed as so-called fiber bursts in dynamic radio spectra, and the results are in good agreement with observed bursts.
By using mouse outcross populations in combination with bioinformatic approaches, it was possible to identify and characterize novel genes regulating body weight, fat mass and β-cell function, which all contribute to the pathogenesis of obesity and T2D. In detail, the presented studies identified 1. Ifi202b/IFI16 as adipogenic gene involved in adipocyte commitment, maintenance of white adipocyte identity, fat cell size and the inflammatory state of adipose tissue. 2. Pla2g4a/PLA2G4A as gene linked to increased body weight and fat mass with a higher expression in adipose tissue of obese mice and pigs as well as in obese human subjects. 3. Ifgga2/IRGM as novel regulator of lipophagy protecting from excess hepatic lipid accumulation. 4. Nidd/DBA as a diabetogenic locus containing Kti12, Osbpl9, Ttc39a and Calr4 with differential expression in pancreatic islets and/or genetic variants. 5. miR-31 to be higher expressed in adipose tissue of obese and diabetic mice and humans targeting PPARy and GLUT4 and thereby involved in adipogenesis and insulin signaling. 6. Gjb4 as novel gene triggering the development of T2D by reducing insulin secretion, inducing apoptosis and inhibiting proliferation. The performed studies confirmed the complexity and strong genetic heritability character of obesity and T2D. A high number of genetic variations, each with a small effect, are collectively influencing the degree and severity of the disease. The use of mouse outcross populations is a valid tool for disease gene identification; however, to facilitate and accelerate the process of gene identification the combination of mouse cross data with advanced sequencing resources and the publicly available data sets are essential. The main goal for future studies should be the translation of these novel molecular discoveries to useful treatment therapies. More recently, several classes of novel unimolecular combination therapeutics have emerged with superior efficacy than currently prescribed options and pose the potential to reverse obesity and T2D (Finan et al., 2015). The glucagon-like peptide-1 (GLP-1)- estrogen conjugate, which targets estrogen into cells expressing GLP-1 receptors, was shown to improve energy, glucose and lipid metabolism as well as to reduce food reward (Finan et al., 2012; Schwenk et al., 2014; Vogel et al., 2016). Another possibility is the development of miRNA-based therapeutics to prevent obesity and T2D, such as miRNA mimetics, anti-miRNA oligonucleotides and exosomes loaded with miRNAs (Ji and Guo, 2019; Gottmann et al., 2020). As already described, genome-wide association studies for polygenic obesity and T2D traits in humans have also led to the identification of numerous gene variants with modest effect, most of them having an unknown function (Yazdi et al., 2015). These discoveries resulted in novel animal models and have illuminated new biologic pathways. Therefore, the integration of mouse-human genetic approaches and the utilization of the synergistic effects have the potential to lead to the identification of more genes responsible for common Mendelian forms of obesity and T2D, as well as gene × gene and gene × environment interactions (Yazdi et al., 2015; Ingelsson and McCarthy, 2018). This combination may help to unravel the missing heritability of obesity and T2D, to identify novel drug targets and to design more efficient and personalized obesity prevention and management programs.
The Arctic plays a key role in Earth’s climate system as global warming is predicted to be most pronounced at high latitudes and because one third of the global carbon pool is stored in ecosystems of the northern latitudes. In order to improve our understanding of the present and future carbon dynamics in climate sensitive permafrost ecosystems, the present study concentrates on investigations of microbial controls of methane fluxes, on the activity and structure of the involved microbial communities, and on their response to changing environmental conditions. For this purpose an integrated research strategy was applied, which connects trace gas flux measurements to soil ecological characterisation of permafrost habitats and molecular ecological analyses of microbial populations. Furthermore, methanogenic archaea isolated from Siberian permafrost have been used as potential keystone organisms for studying and assessing life under extreme living conditions. Long-term studies on methane fluxes were carried out since 1998. These studies revealed considerable seasonal and spatial variations of methane emissions for the different landscape units ranging from 0 to 362 mg m-2 d-1. For the overall balance of methane emissions from the entire delta, the first land cover classification based on Landsat images was performed and applied for an upscaling of the methane flux data sets. The regionally weighted mean daily methane emissions of the Lena Delta (10 mg m-2 d-1) are only one fifth of the values calculated for other Arctic tundra environments. The calculated annual methane emission of the Lena Delta amounts to about 0.03 Tg. The low methane emission rates obtained in this study are the result of the used remotely sensed high-resolution data basis, which provides a more realistic estimation of the real methane emissions on a regional scale. Soil temperature and near soil surface atmospheric turbulence were identified as the driving parameters of methane emissions. A flux model based on these variables explained variations of the methane budget corresponding to continuous processes of microbial methane production and oxidation, and gas diffusion through soil and plants reasonably well. The results show that the Lena Delta contributes significantly to the global methane balance because of its extensive wetland areas. The microbiological investigations showed that permafrost soils are colonized by high numbers of microorganisms. The total biomass is comparable to temperate soil ecosystems. Activities of methanogens and methanotrophs differed significantly in their rates and distribution patterns along both the vertical profiles and the different investigated soils. The methane production rates varied between 0.3 and 38.9 nmol h-1 g-1, while the methane oxidation ranged from 0.2 to 7.0 nmol h-1 g-1. Phylogenetic analyses of methanogenic communities revealed a distinct diversity of methanogens affiliated to Methanomicrobiaceae, Methanosarcinaceae and Methanosaetaceae, which partly form four specific permafrost clusters. The results demonstrate the close relationship between methane fluxes and the fundamental microbiological processes in permafrost soils. The microorganisms do not only survive in their extreme habitat but also can be metabolic active under in situ conditions. It was shown that a slight increase of the temperature can lead to a substantial increase in methanogenic activity within perennially frozen deposits. In case of degradation, this would lead to an extensive expansion of the methane deposits with their subsequent impacts on total methane budget. Further studies on the stress response of methanogenic archaea, especially Methanosarcina SMA-21, isolated from Siberian permafrost, revealed an unexpected resistance of the microorganisms against unfavourable living conditions. A better adaptation to environmental stress was observed at 4 °C compared to 28 °C. For the first time it could be demonstrated that methanogenic archaea from terrestrial permafrost even survived simulated Martian conditions. The results show that permafrost methanogens are more resistant than methanogens from non-permafrost environments under Mars-like climate conditions. Microorganisms comparable to methanogens from terrestrial permafrost can be seen as one of the most likely candidates for life on Mars due to their physiological potential and metabolic specificity.
Proteins are chain molecules built from amino acids. The precise sequence of the 20 different types of amino acids in a protein chain defines into which structure a protein folds, and the three-dimensional structure in turn specifies the biological function of the protein. The reliable folding of proteins is a prerequisite for their robust function. Misfolding can lead to protein aggregates that cause severe diseases, such as Alzheimer's, Parkinson's, or the variant Creutzfeldt-Jakob disease. Small single-domain proteins often fold without experimentally detectable metastable intermediate states. The folding dynamics of these proteins is thought to be governed by a single transition-state barrier between the unfolded and the folded state. The transition state is highly instable and cannot be observed directly. However, mutations in which a single amino acid of the protein is substituted by another one can provide indirect access. The mutations slightly change the transition-state barrier and, thus, the folding and unfolding times of the protein. The central question is how to reconstruct the transition state from the observed changes in folding times. In this habilitation thesis, a novel method to extract structural information on transition states from mutational data is presented. The method is based on (i) the cooperativity of structural elements such as alpha-helices and beta-hairpins, and (ii) on splitting up mutation-induced free-energy changes into components for these elements. By fitting few parameters, the method reveals the degree of structure formation of alpha-helices and beta-hairpins in the transition state. In addition, it is shown in this thesis that the folding routes of small single-domain proteins are dominated by loop-closure dependencies between the structural elements.
Poly(Ionic Liquid)s
(2015)
Our every-day experience is connected with different acoustical noise or music. Usually noise plays the role of nuisance in any communication and destroys any order in a system. Similar optical effects are known: strong snowing or raining decreases quality of a vision. In contrast to these situations noisy stimuli can also play a positive constructive role, e.g. a driver can be more concentrated in a presence of quiet music. Transmission processes in neural systems are of especial interest from this point of view: excitation or information will be transmitted only in the case if a signal overcomes a threshold. Dr. Alexei Zaikin from the Potsdam University studies noise-induced phenomena in nonlinear systems from a theoretical point of view. Especially he is interested in the processes, in which noise influences the behaviour of a system twice: if the intensity of noise is over a threshold, it induces some regular structure that will be synchronized with the behaviour of neighbour elements. To obtain such a system with a threshold one needs one more noise source. Dr. Zaikin has analyzed further examples of such doubly stochastic effects and developed a concept of these new phenomena. These theoretical findings are important, because such processes can play a crucial role in neurophysics, technical communication devices and living sciences.
One of the classical ways to describe the dynamics of nonlinear systems is to analyze theur Fourier spectra. For periodic and quasiperiodic processes the Fourier spectrum consists purely of discrete delta-functions. On the contrary, the spectrum of a chaotic motion is marked by the presence of the continuous component. In this work, we describe the peculiar, neither regular nor completely chaotic state with so called singular-continuous power spectrum. Our investigations concern various cases from most different fields, where one meets the singular continuous (fractal) spectra. The examples include both the physical processes which can be reduced to iterated discrete mappings or even symbolic sequences, and the processes whose description is based on the ordinary or partial differential equations.
The occurrence of earthquakes is characterized by a high degree of spatiotemporal complexity. Although numerous patterns, e.g. fore- and aftershock sequences, are well-known, the underlying mechanisms are not observable and thus not understood. Because the recurrence times of large earthquakes are usually decades or centuries, the number of such events in corresponding data sets is too small to draw conclusions with reasonable statistical significance. Therefore, the present study combines both, numerical modeling and analysis of real data in order to unveil the relationships between physical mechanisms and observational quantities. The key hypothesis is the validity of the so-called "critical point concept" for earthquakes, which assumes large earthquakes to occur as phase transitions in a spatially extended many-particle system, similar to percolation models. New concepts are developed to detect critical states in simulated and in natural data sets. The results indicate that important features of seismicity like the frequency-size distribution and the temporal clustering of earthquakes depend on frictional and structural fault parameters. In particular, the degree of quenched spatial disorder (the "roughness") of a fault zone determines whether large earthquakes occur quasiperiodically or more clustered. This illustrates the power of numerical models in order to identify regions in parameter space, which are relevant for natural seismicity. The critical point concept is verified for both, synthetic and natural seismicity, in terms of a critical state which precedes a large earthquake: a gradual roughening of the (unobservable) stress field leads to a scale-free (observable) frequency-size distribution. Furthermore, the growth of the spatial correlation length and the acceleration of the seismic energy release prior to large events is found. The predictive power of these precursors is, however, limited. Instead of forecasting time, location, and magnitude of individual events, a contribution to a broad multiparameter approach is encouraging.