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This paper develops the incentives to collude in a model with spatially separated markets and quantity setting firms. We find that increases in transportation costs stabilize the collusive agreement. We also show that, the higher the demand in both markets the less likely will collusion be sustained. Gross and Holahan (2003) use a similar model with price setting firms, we compare their results with ours to analyze the impact of the mode of competition on sustainability of collusion. Further we analyze the impact of collusion on social welfare and find that collusion may be welfare enhancing.
Block copolymers are receiving increasing attention in the literature. Reports on amphiphilic block copolymers have now established the basis of their self-assembly behavior: aggregate sizes, morphologies and stability can be explained from the absolute and relative block lengths, the nature of the blocks, the architecture and also solvent selectiveness. In water, self-assembly of amphiphilic block copolymers is assumed to be driven by the hydrophobic. The motivation of this thesis is to study the influence on the self-assembly in water of A b B type block copolymers (with A hydrophilic) of the variation of the hydrophilicity of B from non-soluble (hydrophobic) to totally soluble (hydrophilic). Glucose-modified polybutadiene-block-poly(N-isopropylacrylamide) copolymers were prepared and their self-assembly behavior in water studied. The copolymers formed vesicles with an asymmetric membrane with a glycosylated exterior and poly(N-isopropylacrylamide) on the inside. Above the low critical solution temperature (LCST) of poly(N-isopropylacrylamide), the structure collapsed into micelles with a hydrophobic PNIPAM core and glycosylated exterior. This collapse was found to be reversible. As a result, the structures showed a temperature-dependent interaction with L-lectin proteins and were shown to be able to encapsulate organic molecules. Several families of double hydrophilic block copolymers (DHBC) were prepared. The blocks of these copolymers were biopolymers or polymer chimeras used in aqueous two-phase partition systems. Copolymers based on dextran and poly(ethylene glycol) blocks were able to form aggregates in water. Dex6500-b-PEG5500 copolymer spontaneously formed vesicles with PEG as the “less hydrophilic” barrier and dextran as the solubilizing block. The aggregates were found to be insensitive to the polymer's architecture and concentration (in the dilute range) and only mildly sensitive to temperature. Variation of the block length, yielded different morphologies. A longer PEG chain seemed to promote more curved aggregates following the inverse trend usually observed in amphiphilic block copolymers. A shorter dextran promoted vesicular structures as usually observed for the amphiphilic counterparts. The linking function was shown to have an influence of the morphology but not on the self-assembly capability in itself. The vesicles formed by dex6500-b-PEG5500 showed slow kinetics of clustering in the presence of Con A lectin. In addition both dex6500-b-PEG5500 and its crosslinked derivative were able to encapsulate fluorescent dyes. Two additional dextran-based copolymers were synthesized, dextran-b-poly(vinyl alcohol) and dextran-b-poly(vinyl pyrrolidone). The study of their self-assembly allowed to conclude that aqueous two-phase systems (ATPS) is a valid source of inspiration to conceive DHBCs capable of self-assembling. In the second part the principle was extended to polypeptide systems with the synthesis of a poly(N-hydroxyethylglutamine)-block-poly(ethylene glycol) copolymer. The copolymer that had been previously reported to have emulsifying properties was able to form vesicles by direct dissolution of the solid in water. Last, a series of thermoresponsive copolymers were prepared, dextran-b-PNIPAMm. These polymers formed aggregates below the LCST. Their structure could not be unambiguously elucidated but seemed to correspond to vesicles. Above the LCST, the collapse of the PNIPAM chains induced the formation of stable objects of several hundreds of nanometers in radius that evolved with increasing temperature. The cooling of these solution below LCST restored the initial aggregates. This self-assembly of DHBC outside any stimuli of pH, ionic strength, or temperature has only rarely been described in the literature. This work constituted the first formal attempt to frame the phenomenon. Two reasons were accounted for the self-assembly of such systems: incompatibility of the polymer pairs forming the two blocks (enthalpic) and a considerable solubility difference (enthalpic and entropic). The entropic contribution to the positive Gibbs free energy of mixing is believed to arise from the same loss of conformational entropy that is responsible for “the hydrophobic effect” but driven by a competition for water of the two blocks. In that sense this phenomenon should be described as the “hydrophilic effect”.
The Casimir-Polder interaction between a single neutral atom and a nearby surface, arising from the (quantum and thermal) fluctuations of the electromagnetic field, is a cornerstone of cavity quantum electrodynamics (cQED), and theoretically well established. Recently, Bose-Einstein condensates (BECs) of ultracold atoms have been used to test the predictions of cQED. The purpose of the present thesis is to upgrade single-atom cQED with the many-body theory needed to describe trapped atomic BECs. Tools and methods are developed in a second-quantized picture that treats atom and photon fields on the same footing. We formulate a diagrammatic expansion using correlation functions for both the electromagnetic field and the atomic system. The formalism is applied to investigate, for BECs trapped near surfaces, dispersion interactions of the van der Waals-Casimir-Polder type, and the Bosonic stimulation in spontaneous decay of excited atomic states. We also discuss a phononic Casimir effect, which arises from the quantum fluctuations in an interacting BEC.
Active Galactic Nuclei (AGN) are powered by gas accretion onto supermassive Black Holes (BH). The luminosity of AGN can exceed the integrated luminosity of their host galaxies by orders of magnitude, which are then classified as Quasi-Stellar Objects (QSOs). Some mechanisms are needed to trigger the nuclear activity in galaxies and to feed the nuclei with gas. Among several possibilities, such as gravitational interactions, bar instabilities, and smooth gas accretion from the environment, the dominant process has yet to be identified. Feedback from AGN may be important an important ingredient of the evolution of galaxies. However, the details of this coupling between AGN and their host galaxies remain unclear. In this work we aim to investigate the connection between the AGN and their host galaxies by studying the properties of the extendend ionised gas around AGN. Our study is based on observations of ~50 luminous, low-redshift (z<0.3) QSOs using the novel technique of integral field spectroscopy that combines imaging and spectroscopy. After spatially separating the emission of AGN-ionised gas from HII regions, ionised solely by recently formed massive stars, we demonstrate that the specific star formation rates in several disc-dominated AGN hosts are consistent with those of normal star forming galaxies, while others display no detectable star formation activity. Whether the star formation has been actively suppressed in those particular host galaxies by the AGN, or their gas content is intrinsically low, remains an open question. By studying the kinematics of the ionised gas, we find evidence for non-gravitational motions and outflows on kpc scales only in a few objects. The gas kinematics in the majority of objects however indicate a gravitational origin. It suggests that the importance of AGN feedback may have been overrated in theoretical works, at least at low redshifts. The [OIII] line is the strongest optical emission line for AGN-ionised gas, which can be extended over several kpc scales, usually called the Narrow-Line Region (NLR). We perform a systematic investigation of the NLR size and determine a NLR size-luminosity relation that is consistent with the scenario of a constant ionisation parameter throughout the NLR. We show that previous narrow-band imaging with the Hubble Space Telescope underestimated the NLR size by a factor of >2 and that the continuum AGN luminosity is better correlated with the NLR size than the [OIII] luminosity. These affects may account for the different NLR size-luminosity relations reported in previous studies. On the other hand, we do not detect extended NLRs around all QSOs, and demonstrate that the detection of extended NLRs goes along with radio emission. We employ emission line ratios as a diagnostic for the abundance of heavy elements in the gas, i.e. its metallicity, and find that the radial metallicity gradients are always flatter than in inactive disc-dominated galaxies. This can be interpreted as evidence for radial gas flows from the outskirts of these galaxies to the nucleus. Recent or ongoing galaxy interactions are likely responsible for this effect and may turn out to be a common prerequisite for QSO activity. The metallicity of bulge-dominated hosts are systematically lower than their disc-dominated counterparts, which we interpret as evidence for minor mergers, supported by our detailed study of the bulge-dominated host of the luminous QSO HE 1029-1401, or smooth gas accretion from the environment. In this line another new discovery is that HE 2158-0107 at z=0.218 is the most metal poor luminous QSO ever observed. Together with a large (30kpc) extended structure of low metallicity ionised gas, we propose smooth cold gas accretion as the most likely scenario. Theoretical studies suggested that this process is much more important at earlier epochs of the universe, so that HE 2158-0107 might be an ideal laboratory to study this mechanism of galaxy and BH growth at low redshift more detailed in the furture.
In this thesis, simulations of laser-driven many-electron dynamics in molecules are presented, i.e., the interaction between molecules and an electromagnetic field is demonstrated. When a laser field is applied to a molecular system, a population of higher electronic states takes place as well as other processes, e.g. photoionization, which is described by an appropriate model. Also, a finite lifetime of an excited state can be described by such a model. In the second part, a method is postulated that is capable of describing electron correlation in a time-dependent scheme. This is done by introducing a single-electron entropy that is at least temporarily minimized in a further step.
The lakes of the East African Rift System (EARS) have been intensively studied to better understand the influence of climate change on hydrological systems. The exceptional sensitivity of these rift lakes, however, is both a challenge and an opportunity when trying to reconstruct past climate changes from changes in the hydrological budget of lake basins on timescales 100 to 104 years. On one hand, differences in basin geometrics (shape, area, volume, depth), catchment rainfall distributions and varying erosion-deposition rates complicate regional interpretation of paleoclimate information from lacustrine sediment proxies. On the other hand, the sensitivity of rift lakes often provides paleoclimate records of excellent quality characterized by a high signal-to-noise ratio. This study aims at better understanding of the climate-proxy generating process in rift lakes by parameterizing the geomorphological and hydroclimatic conditions of a particular site providing a step towards the establishment of regional calibrations of transfer functions for climate reconstructions. The knowledge of the sensitivity of a lake basin to climate change furthermore is crucial for a better assessment of the probability of catastrophic changes in the future, which bear risks for landscapes, ecosystems, and organisms of all sorts, including humans. Part 1 of this thesis explores the effect of the morphology and the effective moisture of a lake catchment. The availability of digital elevation models (DEM) and gridded climate data sets facilitates the comparison of the morphological and hydroclimatic conditions of rift lakes. I used the hypsometric integral (HI) calculated from Shuttle Radar Topography Mission (SRTM) data to describe the morphology of ten lake basins in Kenya and Ethiopia. The aridity index (AI) describing the difference in the precipitation/evaporation balance within a catchment was used to compare the hydroclimatic of these basins. Correlating HI and AI with published Holocene lake-level variations revealed that lakes responding sensitively to relatively moderate climate change are typically graben shaped and characterized by a HI between 0.23-0.30, and relatively humid conditions with AI >1. These amplifier lakes, a term first introduced but not fully parameterized by Alayne Street-Perrott in the early 80s, are unexceptionally located in the crest of the Kenyan and Ethiopian domes. The non-amplifier lakes in the EARS either have lower HI 0.13-0.22 and higher AI (>1) or higher HI (0.31-0.37) and low AI (<1), reflecting pan-shaped morphologies with more arid hydroclimatic conditions. Part 2 of this work addresses the third important factor to be considered when using lake-level and proxy records to unravel past climate changes in the EARS: interbasin connectivity and groundwater flow through faulted and porous subsurface lithologies in a rift setting. First, I have compiled the available hydrogeological data including lithology, resistivity and water-well data for the adjacent Naivasha and Elmenteita-Nakuru basins in the Central Kenya Rift. Using this subsurface information and established records of lake-level decline at the last wet-dry climate transitions, i.e., the termination of the African Humid Period (AHP, 15 to 5 kyr BP), I used a linear decay model to estimate typical groundwater flow between the two basins. The results suggest a delayed response of the groundwater levels of ca. 5 kyrs if no recharge of groundwater occurs during the wet-dry transition, whereas the lag is 2-2.7 kyrs only using the modern recharge of ca. 0.52 m/yr. The estimated total groundwater flow from higher Lake Naivasha (1,880 m a.s.l. during the AHP) to Nakuru-Elmenteita (1,770 m) was 40 cubic kilometers. The unexpectedly large volume, more than half of the volume of the paleo-Lake Naivasha during the Early Holocene, emphasizes the importance of groundwater in hydrological modeling of paleo-lakes in rifts. Moreover, the subsurface connectivity of rift lakes also causes a significant lag time to the system introducing a nonlinear component to the system that has to be considered while interpreting paleo-lake records. Part 3 of this thesis investigated the modern intraseasonal precipitation variability within eleven lake basins discussed in the first section of the study excluding Lake Victoria and including Lake Tana. Remotely sensed rainfall estimates (RFE) from FEWS NET for 1996-2010, are used for the, March April May (MAM) July August September (JAS), October November (ON) and December January February (DJF). The seasonal precipitation are averaged and correlated with the prevailing regional and local climatic mechanisms. Results show high variability with Biennial to Triennial precipitation patterns. The spatial distribution of precipitation in JAS are linked to the onset and strength of the Congo Air Boundary (CAB) and Indian Summer Monsoon (ISM) dynamics. while in ON they are related to the strength of Positive ENSO and IOD phases This study describes the influence of graben morphologies, extreme climate constrasts within catchments and basins connectivity through faults and porous lithologies on rift lakes. Hence, it shows the importance of a careful characterization of a rift lake by these parameters prior to concluding from lake-level and proxy records to climate changes. Furthermore, this study highlights the exceptional sensitivity of rift lakes to relatively moderate climate change and its consequences for water availability to the biosphere including humans.
Soil moisture is a key state variable that controls runoff formation, infiltration and partitioning of radiation into latent and sensible heat. However, the experimental characterisation of near surface soil moisture patterns and their controls on runoff formation remains a challenge. This subject was one aspect of the BMBF-funded OPAQUE project (operational discharge and flooding predictions in head catchments). As part of that project the focus of this dissertation is on: (1) testing the methodology and feasibility of the Spatial TDR technology in producing soil moisture profiles along TDR probes, including an inversion technique of the recorded signal in heterogeneous field soils, (2) the analysis of spatial variability and temporal dynamics of soil moisture at the field scale including field experiments and hydrological modelling, (3) the application of models of different complexity for understanding soil moisture dynamics and its importance for runoff generation as well as for improving the prediction of runoff volumes. To fulfil objective 1, several laboratory experiments were conducted to understand the influence of probe rod geometry and heterogeneities in the sampling volume under different wetness conditions. This includes a detailed analysis on how these error sources affect retrieval of soil moisture profiles in soils. Concerning objective 2 a sampling strategy of two TDR clusters installed in the head water of the Wilde Weißeritz catchment (Eastern Ore Mountains, Germany) was used to investigate how well “the catchment state” can be characterised by means of distributed soil moisture data observed at the field scale. A grassland site and a forested site both located on gentle slopes were instrumented with two Spatial TDR clusters that consist of up to 39 TDR probes. Process understanding was gained by modelling the interaction of evapotranspiration and soil moisture with the hydrological process model CATFLOW. A field scale irrigation experiment was carried out to investigate near subsurface processes at the hillslope scale. The interactions of soil moisture and runoff formation were analysed using discharge data from three nested catchments: the Becherbach with a size of 2 km², the Rehefeld catchment (17 km²) and the superordinate Ammelsdorf catchment (49 km²). Statistical analyses including observations of pre-event runoff, soil moisture and different rainfall characteristics were employed to predict stream flow volume. On the different scales a strong correlation between the average soil moisture and the runoff coefficients of rainfall-runoff events could be found, which almost explains equivalent variability as the pre-event runoff. Furthermore, there was a strong correlation between surface soil moisture and subsurface wetness with a hysteretic behaviour between runoff soil moisture. To fulfil objective 3 these findings were used in a generalised linear model (GLM) analysis which combines state variables describing the catchments antecedent wetness and variables describing the meteorological forcing in order to predict event runoff coefficients. GLM results were compared to simulations with the catchment model WaSiM ETH. Hereby were the model results of the GLMs always better than the simulations with WaSiM ETH. The GLM analysis indicated that the proposed sampling strategy of clustering TDR probes in typical functional units is a promising technique to explore soil moisture controls on runoff generation and can be an important link between the scales. Long term monitoring of such sites could yield valuable information for flood warning and forecasting by identifying critical soil moisture conditions for the former and providing a better representation of the initial moisture conditions for the latter.
Supermassive black holes are a fundamental component of the universe in general and of galaxies in particular. Almost every massive galaxy harbours a supermassive black hole (SMBH) in its center. Furthermore, there is a close connection between the growth of the SMBH and the evolution of its host galaxy, manifested in the relationship between the mass of the black hole and various properties of the galaxy's spheroid component, like its stellar velocity dispersion, luminosity or mass. Understanding this relationship and the growth of SMBHs is essential for our picture of galaxy formation and evolution. In this thesis, I make several contributions to improve our knowledge on the census of SMBHs and on the coevolution of black holes and galaxies. The first route I follow on this road is to obtain a complete census of the black hole population and its properties. Here, I focus particularly on active black holes, observable as Active Galactic Nuclei (AGN) or quasars. These are found in large surveys of the sky. In this thesis, I use one of these surveys, the Hamburg/ESO survey (HES), to study the AGN population in the local volume (z~0). The demographics of AGN are traditionally represented by the AGN luminosity function, the distribution function of AGN at a given luminosity. I determined the local (z<0.3) optical luminosity function of so-called type 1 AGN, based on the broad band B_J magnitudes and AGN broad Halpha emission line luminosities, free of contamination from the host galaxy. I combined this result with fainter data from the Sloan Digital Sky Survey (SDSS) and constructed the best current optical AGN luminosity function at z~0. The comparison of the luminosity function with higher redshifts supports the current notion of 'AGN downsizing', i.e. the space density of the most luminous AGN peaks at higher redshifts and the space density of less luminous AGN peaks at lower redshifts. However, the AGN luminosity function does not reveal the full picture of active black hole demographics. This requires knowledge of the physical quantities, foremost the black hole mass and the accretion rate of the black hole, and the respective distribution functions, the active black hole mass function and the Eddington ratio distribution function. I developed a method for an unbiased estimate of these two distribution functions, employing a maximum likelihood technique and fully account for the selection function. I used this method to determine the active black hole mass function and the Eddington ratio distribution function for the local universe from the HES. I found a wide intrinsic distribution of black hole accretion rates and black hole masses. The comparison of the local active black hole mass function with the local total black hole mass function reveals evidence for 'AGN downsizing', in the sense that in the local universe the most massive black holes are in a less active stage then lower mass black holes. The second route I follow is a study of redshift evolution in the black hole-galaxy relations. While theoretical models can in general explain the existence of these relations, their redshift evolution puts strong constraints on these models. Observational studies on the black hole-galaxy relations naturally suffer from selection effects. These can potentially bias the conclusions inferred from the observations, if they are not taken into account. I investigated the issue of selection effects on type 1 AGN samples in detail and discuss various sources of bias, e.g. an AGN luminosity bias, an active fraction bias and an AGN evolution bias. If the selection function of the observational sample and the underlying distribution functions are known, it is possible to correct for this bias. I present a fitting method to obtain an unbiased estimate of the intrinsic black hole-galaxy relations from samples that are affected by selection effects. Third, I try to improve our census of dormant black holes and the determination of their masses. One of the most important techniques to determine the black hole mass in quiescent galaxies is via stellar dynamical modeling. This method employs photometric and kinematic observations of the galaxy and infers the gravitational potential from the stellar orbits. This method can reveal the presence of the black hole and give its mass, if the sphere of the black hole's gravitational influence is spatially resolved. However, usually the presence of a dark matter halo is ignored in the dynamical modeling, potentially causing a bias on the determined black hole mass. I ran dynamical models for a sample of 12 galaxies, including a dark matter halo. For galaxies for which the black hole's sphere of influence is not well resolved, I found that the black hole mass is systematically underestimated when the dark matter halo is ignored, while there is almost no effect for galaxies with well resolved sphere of influence.
Conventional energy sources are diminishing and non-renewable, take million years to form and cause environmental degradation. In the 21st century, we have to aim at achieving sustainable, environmentally friendly and cheap energy supply by employing renewable energy technologies associated with portable energy storage devices. Lithium-ion batteries can repeatedly generate clean energy from stored materials and convert reversely electric into chemical energy. The performance of lithium-ion batteries depends intimately on the properties of their materials. Presently used battery electrodes are expensive to be produced; they offer limited energy storage possibility and are unsafe to be used in larger dimensions restraining the diversity of application, especially in hybrid electric vehicles (HEVs) and electric vehicles (EVs). This thesis presents a major progress in the development of LiFePO4 as a cathode material for lithium-ion batteries. Using simple procedure, a completely novel morphology has been synthesized (mesocrystals of LiFePO4) and excellent electrochemical behavior was recorded (nanostructured LiFePO4). The newly developed reactions for synthesis of LiFePO4 are single-step processes and are taking place in an autoclave at significantly lower temperature (200 deg. C) compared to the conventional solid-state method (multi-step and up to 800 deg. C). The use of inexpensive environmentally benign precursors offers a green manufacturing approach for a large scale production. These newly developed experimental procedures can also be extended to other phospho-olivine materials, such as LiCoPO4 and LiMnPO4. The material with the best electrochemical behavior (nanostructured LiFePO4 with carbon coating) was able to delive a stable 94% of the theoretically known capacity.
Corvino, Corvino and Schoen, Chruściel and Delay have shown the existence of a large class of asymptotically flat vacuum initial data for Einstein's field equations which are static or stationary in a neighborhood of space-like infinity, yet quite general in the interior. The proof relies on some abstract, non-constructive arguments which makes it difficult to calculate such data numerically by using similar arguments. A quasilinear elliptic system of equations is presented of which we expect that it can be used to construct vacuum initial data which are asymptotically flat, time-reflection symmetric, and asymptotic to static data up to a prescribed order at space-like infinity. A perturbation argument is used to show the existence of solutions. It is valid when the order at which the solutions approach staticity is restricted to a certain range. Difficulties appear when trying to improve this result to show the existence of solutions that are asymptotically static at higher order. The problems arise from the lack of surjectivity of a certain operator. Some tensor decompositions in asymptotically flat manifolds exhibit some of the difficulties encountered above. The Helmholtz decomposition, which plays a role in the preparation of initial data for the Maxwell equations, is discussed as a model problem. A method to circumvent the difficulties that arise when fast decay rates are required is discussed. This is done in a way that opens the possibility to perform numerical computations. The insights from the analysis of the Helmholtz decomposition are applied to the York decomposition, which is related to that part of the quasilinear system which gives rise to the difficulties. For this decomposition analogous results are obtained. It turns out, however, that in this case the presence of symmetries of the underlying metric leads to certain complications. The question, whether the results obtained so far can be used again to show by a perturbation argument the existence of vacuum initial data which approach static solutions at infinity at any given order, thus remains open. The answer requires further analysis and perhaps new methods.
The northward movement and collision of the Arabian plate with Eurasia generates compressive stresses and resulting shortening in Iran. Within the Alborz Mountains, North Iran, a complex and not well understood system of strike-slip and thrust faults accomodates a fundamental part of the NNE-SSW oriented shortening. On 28th of May 2004 the Mw 6.3 Baladeh earthquake hit the north-central Alborz Mountains. It is one of the rare and large events in this region in modern time and thus a seldom chance to study earthquake mechanisms and the local ongoing deformation processes. It also demonstrated the high vulnerability of this densily populated region.
Unique column combinations of a relational database table are sets of columns that contain only unique values. Discovering such combinations is a fundamental research problem and has many different data management and knowledge discovery applications. Existing discovery algorithms are either brute force or have a high memory load and can thus be applied only to small datasets or samples. In this paper, the wellknown GORDIAN algorithm and "Apriori-based" algorithms are compared and analyzed for further optimization. We greatly improve the Apriori algorithms through efficient candidate generation and statistics-based pruning methods. A hybrid solution HCAGORDIAN combines the advantages of GORDIAN and our new algorithm HCA, and it significantly outperforms all previous work in many situations.
The transcriptional regulation of the cellular mechanisms involves many different components and different levels of control which together contribute to fine tune the response of cells to different environmental stimuli. In some responses, diverse signaling pathways can be controlled simultaneously. One of the most important cellular processes that seem to possess multiple levels of regulation is photosynthesis. A model organism for studying photosynthesis-related processes is the unicellular green algae Chlamydomonas reinhardtii, due to advantages related to culturing, genetic manipulation and availability of genome sequence. In the present study, we were interested in understanding the regulatory mechanisms underlying photosynthesis-related processes. To achieve this goal different molecular approaches were followed. In order to indentify protein transcriptional regulators we optimized a method for isolation of nuclei and performed nuclear proteome analysis using shotgun proteomics. This analysis permitted us to improve the genome annotation previously published and to discover conserved and enriched protein motifs among the nuclear proteins. In another approach, a quantitative RT-PCR platform was established for the analysis of gene expression of predicted transcription factor (TF) and other transcriptional regulator (TR) coding genes by transcript profiling. The gene expression profiles for more than one hundred genes were monitored in time series experiments under conditions of changes in light intensity (200 µE m-2 s-1 to 700 µE m-2 s-1), and changes in concentration of carbon dioxide (5% CO2 to 0.04% CO2). The results indicate that many TF and TR genes are regulated in both environmental conditions and groups of co-regulated genes were found. Our findings also suggest that some genes can be common intermediates of light and carbon responsive regulatory pathways. These approaches together gave us new insights about the regulation of photosynthesis and revealed new candidate regulatory genes, helping to decipher the gene regulatory networks in Chlamydomonas. Further experimental studies are necessary to clarify the function of the candidate regulatory genes and to elucidate how cells coordinately regulate the assimilation of carbon and light responses.
Plants and some unicellular algae store carbon in the form of transitory starch on a diurnal basis. The turnover of this glucose polymer is tightly regulated and timely synthesis as well as mobilization is essential to provide energy for heterotrophic growth. Especially for starch degradation, novel enzymes and mechanisms have been proposed recently. However, the catalytic properties of these enzymes and their coordination with metabolic regulation are still to be discovered. This thesis develops theoretical methods in order to interpret and analyze enzymes and their role in starch degradation. In the first part, a novel description of interfacial enzyme catalysis is proposed. Since the initial steps of starch degradation involve reactions at the starch-stroma interface it is necessary to have a framework which allows the derivation of interfacial enzyme rate laws. A cornerstone of the method is the introduction of the available area function - a concept from surface physics - to describe the adsorption step in the catalytic cycle. The method is applied to derive rate laws for two hydrolases, the Beta-amylase (BAM3) and the Isoamylase (DBE/ISA3), as well as to the Glucan, water dikinase (GWD) and a Phosphoglucan phosphatase (DSP/SEX4). The second part uses the interfacial rate laws to formulate a kinetic model of starch degradation. It aims at reproducing the stimulatory effect of reversible phosphorylation by GWD and DSP on the breakdown of the granule. The model can describe the dynamics of interfacial properties during degradation and suggests that interfacial amylopectin side-chains undergo spontaneous helix-coil transitions. Reversible phosphorylation has a synergistic effect on glucan release especially in the early phase dropping off during degradation. Based on the model, the hypothesis is formulated that interfacial phosphorylation is important for the rapid switch from starch synthesis to starch degradation. The third part takes a broader perspective on carbohydrate-active enzymes (CAZymes) but is motivated by the organization of the downstream pathway of starch breakdown. This comprises Alpha-1,4-glucanotransferases (DPE1 and DPE2) and Alpha-glucan-phosphorylases (Pho or PHS) both in the stroma and in the cytosol. CAZymes accept many different substrates and catalyze numerous reactions and therefore cannot be characterized in classical enzymological terms. A concise characterization is provided by conceptually linking statistical thermodynamics and polymer biochemistry. Each reactant is interpreted as an energy level, transitions between which are constrained by the enzymatic mechanisms. Combinations of in vitro assays of polymer-active CAZymes essential for carbon metabolism in plants confirmed the dominance of entropic gradients. The principle of entropy maximization provides a generalization of the equilibrium constant. Stochastic simulations confirm the results and suggest that randomization of metabolites in the cytosolic pool of soluble heteroglycans (SHG) may contribute to a robust integration of fluctuating carbon fluxes coming from chloroplasts.
Aggregation of the Amyloid β (Aβ) peptide to amyloid fibrils is associated with the outbreak of Alzheimer’s disease. Early aggregation intermediates in form of soluble oligomers are of special interest as they are believed to be the major toxic components in the process. These oligomers are of disordered and transient nature. Therefore, their detailed molecular structure is difficult to access experimentally and often remains unknown. In the present work extensive, fully atomistic replica exchange molecular dynamics simulations were performed to study the preaggregated, monomer states and early aggregation intermediates (dimers, trimers) of Aβ(25-35) and Aβ(10-35)-NH2 in aqueous solution. The folding and aggregation of Aβ(25-35) were studied at neutral pH and 293 K. Aβ(25-35) monomers mainly adopt β-hairpin conformations characterized by a β-turn formed by residues G29 and A30, and a β-sheet between residues N27–K28 and I31–I32 in equilibrium with coiled conformations. The β-hairpin conformations served as initial configurations to model spontaneous aggregation of Aβ(25-35). As expected, within the Aβ(25-35) dimer and trimer ensembles many different poorly populated conformations appear. Nevertheless, we were able to distinguish between disordered and fibril-like oligomers. Whereas disordered oligomers are rather compact with few intermolecular hydrogen bonds (HBs), fibril-like oligomers are characterized by the formation of large intermolecular β-sheets. In most of the fibril-like dimers and trimers individual peptides are fully extended forming in- or out-of-register antiparallel β-sheets. A small amount of fibril-like trimers contained V-shaped peptides forming parallel β-sheets. The dimensions of extended and V-shaped oligomers correspond well to the diameters of two distinct morphologies found for Aβ(25-35) fibrils. The transition from disordered to fibril-like Aβ(25-35) dimers is unfavorable but driven by energy. The lower energy of fibril-like dimers arises from favorable intermolecular HBs and other electrostatic interactions which compete with a loss in entropy. Approximately 25 % of the entropic cost correspond to configurational entropy. The rest relates to solvent entropy, presumably caused by hydrophobic and electrostatic effects. In contrast to the transition towards fibril-like dimers the first step of aggregation is driven by entropy. Here, we compared structural and thermodynamic properties of the individual monomer, dimer and trimer ensembles to gain qualitative information about the aggregation process. The β-hairpin conformation observed for monomers is successively dissolved in dimer and trimer ensembles while instead intermolecular β-sheets are formed. As expected upon aggregation the configurational entropy decreases. Additionally, the solvent accessible surface area (SASA), especially the hydrophobic SASA, decreases yielding a favorable solvation free energy which overcompensates the loss in configurational entropy. In summary, the hydrophobic effect, possibly combined with electrostatic effects, yields an increase in solvent entropy which is believed to be one major driving force towards aggregation. Spontaneous folding of the Aβ(10-35)-NH2 monomer was modeled using two force fields, GROMOS96 43a1 and OPLS/AA, and compared to primary NMR data collected at pH 5.6 and 283 K taken from the literature. Unexpectedly, the two force fields yielded significantly different main conformations. Comparison between experimental and calculated nuclear Overhauser effect (NOE) distances is not sufficient to distinguish between the different force fields. Additionally, the comparison with scalar coupling constants suggest that the chosen protonation in both simulations corresponds to a pH lower than in the experiment. Based on this analysis we were unable to determine which force field yields a better description of this system. Dimerization of Aβ(10-35)-NH2 was studied at neutral pH and 300 K. Dimer conformations arrange in many distinct, poorly populated and rather complex alignments or interlocking patterns which are rather stabilized by side chain interactions than by specific intermolecular hydrogen bonds. Similar to Aβ(25-35) dimers, transition towards β-sheet-rich, fibril-like Aβ(10-35) dimers is driven by energy competing with a loss in entropy. Here, transition is mediated by favorable peptide-solvent and solvent-solvent interactions mainly arising from electrostatic interactions.
Looking at smoking-behavior it can be shown that there are differences concerning the time-preference-rate. Therefore this has an effect on the optimal schooling decision in the way that we appear a lower average human capital level for smokers. According to a higher time-preference-rate additionally we suppose a higher return to education for smokers who go further on education. With our empirical findings we can confirm the presumptions. We use interactions-terms to regress the average rate of return with IV. Therefore we obtain that smokers have a significantly higher average return to education than non-smokers.
The use of nano zerovalent iron (nZVI) for environmental remediation is a promising new technique for in situ remediation. Due to its high surface area and high reactivity, nZVI is able to dechlorinate organic contaminants and render them harmless. Limited mobility, due to fast aggregation and sedimentation of nZVI, limits the capability for source and plume remediation. Carbo-Iron is a newly developed material consisting of activated carbon particles (d50 = 0,8 µm) that are plated with nZVI particles. These particles combine the mobility of activated carbon and the reactivity of nZVI. This paper presents the first results of the transport experiments.
In the living cell, the organization of the complex internal structure relies to a large extent on molecular motors. Molecular motors are proteins that are able to convert chemical energy from the hydrolysis of adenosine triphosphate (ATP) into mechanical work. Being about 10 to 100 nanometers in size, the molecules act on a length scale, for which thermal collisions have a considerable impact onto their motion. In this way, they constitute paradigmatic examples of thermodynamic machines out of equilibrium. This study develops a theoretical description for the energy conversion by the molecular motor myosin V, using many different aspects of theoretical physics. Myosin V has been studied extensively in both bulk and single molecule experiments. Its stepping velocity has been characterized as a function of external control parameters such as nucleotide concentration and applied forces. In addition, numerous kinetic rates involved in the enzymatic reaction of the molecule have been determined. For forces that exceed the stall force of the motor, myosin V exhibits a 'ratcheting' behaviour: For loads in the direction of forward stepping, the velocity depends on the concentration of ATP, while for backward loads there is no such influence. Based on the chemical states of the motor, we construct a general network theory that incorporates experimental observations about the stepping behaviour of myosin V. The motor's motion is captured through the network description supplemented by a Markov process to describe the motor dynamics. This approach has the advantage of directly addressing the chemical kinetics of the molecule, and treating the mechanical and chemical processes on equal grounds. We utilize constraints arising from nonequilibrium thermodynamics to determine motor parameters and demonstrate that the motor behaviour is governed by several chemomechanical motor cycles. In addition, we investigate the functional dependence of stepping rates on force by deducing the motor's response to external loads via an appropriate Fokker-Planck equation. For substall forces, the dominant pathway of the motor network is profoundly different from the one for superstall forces, which leads to a stepping behaviour that is in agreement with the experimental observations. The extension of our analysis to Markov processes with absorbing boundaries allows for the calculation of the motor's dwell time distributions. These reveal aspects of the coordination of the motor's heads and contain direct information about the backsteps of the motor. Our theory provides a unified description for the myosin V motor as studied in single motor experiments.
In the present thesis, the self-assembly of multi thermoresponsive block copolymers in dilute aqueous solution was investigated by a combination of turbidimetry, dynamic light scattering, TEM measurements, NMR as well as fluorescence spectroscopy. The successive conversion of such block copolymers from a hydrophilic into a hydrophobic state includes intermediate amphiphilic states with a variable hydrophilic-to-lipophilic balance. As a result, the self-organization is not following an all-or-none principle but a multistep aggregation in dilute solution was observed. The synthesis of double thermoresponsive diblock copolymers as well as triple thermoresponsive triblock copolymers was realized using twofold-TMS labeled RAFT agents which provide direct information about the average molar mass as well as residual end group functionality from a routine proton NMR spectrum. First a set of double thermosensitive diblock copolymers poly(N-n-propylacrylamide)-b-poly(N-ethylacrylamide) was synthesized which differed only in the relative size of the two blocks. Depending on the relative block lengths, different aggregation pathways were found. Furthermore, the complementary TMS-labeled end groups served as NMR-probes for the self-assembly of these diblock copolymers in dilute solution. Reversible, temperature sensitive peak splitting of the TMS-signals in NMR spectroscopy was indicative for the formation of mixed star-/flower-like micelles in some cases. Moreover, triple thermoresponsive triblock copolymers from poly(N-n-propylacrylamide) (A), poly(methoxydiethylene glycol acrylate) (B) and poly(N-ethylacrylamide) (C) were obtained from sequential RAFT polymerization in all possible block sequences (ABC, BAC, ACB). Their self-organization behavior in dilute aqueous solution was found to be rather complex and dependent on the positioning of the different blocks within the terpolymers. Especially the localization of the low-LCST block (A) had a large influence on the aggregation behavior. Above the first cloud point, aggregates were only observed when the A block was located at one terminus. Once placed in the middle, unimolecular micelles were observed which showed aggregation only above the second phase transition temperature of the B block. Carrier abilities of such triple thermosensitive triblock copolymers tested in fluorescence spectroscopy, using the solvatochromic dye Nile Red, suggested that the hydrophobic probe is less efficiently incorporated by the polymer with the BAC sequence as compared to ABC or ACB polymers above the first phase transition temperature. In addition, due to the problem of increasing loss of end group functionality during the subsequent polymerization steps, a novel concept for the one-step synthesis of multi thermoresponsive block copolymers was developed. This allowed to synthesize double thermoresponsive di- and triblock copolymers in a single polymerization step. The copolymerization of different N-substituted maleimides with a thermosensitive styrene derivative (4-vinylbenzyl methoxytetrakis(oxyethylene) ether) led to alternating copolymers with variable LCST. Consequently, an excess of this styrene-based monomer allowed the synthesis of double thermoresponsive tapered block copolymers in a single polymerization step.