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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.
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 modeling and evaluation calculus FMC-QE, the Fundamental Modeling Concepts for Quanti-tative Evaluation [1], extends the Fundamental Modeling Concepts (FMC) for performance modeling and prediction. In this new methodology, the hierarchical service requests are in the main focus, because they are the origin of every service provisioning process. Similar to physics, these service requests are a tuple of value and unit, which enables hierarchical service request transformations at the hierarchical borders and therefore the hierarchical modeling. Through reducing the model complexity of the models by decomposing the system in different hierarchical views, the distinction between operational and control states and the calculation of the performance values on the assumption of the steady state, FMC-QE has a scalable applica-bility on complex systems. According to FMC, the system is modeled in a 3-dimensional hierarchical representation space, where system performance parameters are described in three arbitrarily fine-grained hierarchi-cal bipartite diagrams. The hierarchical service request structures are modeled in Entity Relationship Diagrams. The static server structures, divided into logical and real servers, are de-scribed as Block Diagrams. The dynamic behavior and the control structures are specified as Petri Nets, more precisely Colored Time Augmented Petri Nets. From the structures and pa-rameters of the performance model, a hierarchical set of equations is derived. The calculation of the performance values is done on the assumption of stationary processes and is based on fundamental laws of the performance analysis: Little's Law and the Forced Traffic Flow Law. Little's Law is used within the different hierarchical levels (horizontal) and the Forced Traffic Flow Law is the key to the dependencies among the hierarchical levels (vertical). This calculation is suitable for complex models and allows a fast (re-)calculation of different performance scenarios in order to support development and configuration decisions. Within the Research Group Zorn at the Hasso Plattner Institute, the work is embedded in a broader research in the development of FMC-QE. While this work is concentrated on the theoretical background, description and definition of the methodology as well as the extension and validation of the applicability, other topics are in the development of an FMC-QE modeling and evaluation tool and the usage of FMC-QE in the design of an adaptive transport layer in order to fulfill Quality of Service and Service Level Agreements in volatile service based environments. This thesis contains a state-of-the-art, the description of FMC-QE as well as extensions of FMC-QE in representative general models and case studies. In the state-of-the-art part of the thesis in chapter 2, an overview on existing Queueing Theory and Time Augmented Petri Net models and other quantitative modeling and evaluation languages and methodologies is given. Also other hierarchical quantitative modeling frameworks will be considered. The description of FMC-QE in chapter 3 consists of a summary of the foundations of FMC-QE, basic definitions, the graphical notations, the FMC-QE Calculus and the modeling of open queueing networks as an introductory example. The extensions of FMC-QE in chapter 4 consist of the integration of the summation method in order to support the handling of closed networks and the modeling of multiclass and semaphore scenarios. Furthermore, FMC-QE is compared to other performance modeling and evaluation approaches. In the case study part in chapter 5, proof-of-concept examples, like the modeling of a service based search portal, a service based SAP NetWeaver application and the Axis2 Web service framework will be provided. Finally, conclusions are given by a summary of contributions and an outlook on future work in chapter 6. [1] Werner Zorn. FMC-QE - A New Approach in Quantitative Modeling. In Hamid R. Arabnia, editor, Procee-dings of the International Conference on Modeling, Simulation and Visualization Methods (MSV 2007) within WorldComp ’07, pages 280 – 287, Las Vegas, NV, USA, June 2007. CSREA Press. ISBN 1-60132-029-9.
Does it have to be trees? : Data-driven dependency parsing with incomplete and noisy training data
(2011)
We present a novel approach to training data-driven dependency parsers on incomplete annotations. Our parsers are simple modifications of two well-known dependency parsers, the transition-based Malt parser and the graph-based MST parser. While previous work on parsing with incomplete data has typically couched the task in frameworks of unsupervised or semi-supervised machine learning, we essentially treat it as a supervised problem. In particular, we propose what we call agnostic parsers which hide all fragmentation in the training data from their supervised components. We present experimental results with training data that was obtained by means of annotation projection. Annotation projection is a resource-lean technique which allows us to transfer annotations from one language to another within a parallel corpus. However, the output tends to be noisy and incomplete due to cross-lingual non-parallelism and error-prone word alignments. This makes the projected annotations a suitable test bed for our fragment parsers. Our results show that (i) dependency parsers trained on large amounts of projected annotations achieve higher accuracy than the direct projections, and that (ii) our agnostic fragment parsers perform roughly on a par with the original parsers which are trained only on strictly filtered, complete trees. Finally, (iii) when our fragment parsers are trained on artificially fragmented but otherwise gold standard dependencies, the performance loss is moderate even with up to 50% of all edges removed.
Rainfall, snow-, and glacial melt throughout the Himalaya control river discharge, which is vital for maintaining agriculture, drinking water and hydropower generation. However, the spatiotemporal contribution of these discharge components to Himalayan rivers is not well understood, mainly because of the scarcity of ground-based observations. Consequently, there is also little known about the triggers and sources of peak sediment flux events, which account for extensive hydropower reservoir filling and turbine abrasion. We therefore lack basic information on the distribution of water resources and controls of erosion processes. In this thesis, I employ various methods to assess and quantify general characteristics of and links between precipitation, river discharge, and sediment flux in the Sutlej Valley. First, I analyze daily precipitation data (1998-2007) from 80 weather stations in the western Himalaya, to decipher the distribution of rain- and snowfall. Rainfall magnitude frequency analyses indicate that 40% of the summer rainfall budget is attributed to monsoonal rainstorms, which show higher variability in the orogenic interior than in frontal regions. Combined analysis of rainstorms and sediment flux data of a major Sutlej River tributary indicate that monsoonal rainfall has a first order control on erosion processes in the orogenic interior, despite the dominance of snowfall in this region. Second, I examine the contribution of rainfall, snow and glacial melt to river discharge in the Sutlej Valley (s55,000 km2), based on a distributed hydrological model, which covers the period 2000-2008. To achieve high spatial and daily resolution despite limited ground-based observations the hydrological model is forced by daily remote sensing data, which I adjusted and calibrated with ground station data. The calibration shows that the Tropical Rainfall Measuring Mission (TRMM) 3B42 rainfall product systematically overestimates rainfall in semi-arid and arid regions, increasing with aridity. The model results indicate that snowmelt-derived discharge (74%) is most important during the pre-monsoon season (April to June) whereas rainfall (56%) and glacial melt (17%) dominate the monsoon season (July-September). Therefore, climate change most likely causes a reduction in river discharge during the pre-monsoon season, which especially affects the orogenic interior. Third, I investigate the controls on suspended sediment flux in different parts of the Sutlej catchments, based on daily gauging data from the past decade. In conjunction with meteorological data, earthquake records, and rock strength measurements I find that rainstorms are the most frequent trigger of high-discharge events with peaks in suspended sediment concentrations (SSC) that account for the bulk of the suspended sediment flux. The suspended sediment flux increases downstream, mainly due to increases in runoff. Pronounced erosion along the Himalayan Front occurs throughout the monsoon season, whereas efficient erosion of the orogenic interior is confined to single extreme events. The results of this thesis highlight the importance of snow and glacially derived melt waters in the western Himalaya, where extensive regions receive only limited amounts of monsoonal rainfall. These regions are therefore particularly susceptible to global warming with major implications on the hydrological cycle. However, the sediment discharge data show that infrequent monsoonal rainstorms that pass the orographic barrier of the Higher Himalaya are still the primary trigger of the highest-impact erosion events, despite being subordinate to snow and glacially–derived discharge. These findings may help to predict peak sediment flux events and could underpin the strategic development of preventative measures for hydropower infrastructures.
The East African Plateau provides a spectacular example of geodynamic plateau uplift, active continental rifting, and associated climatic forcing. It is an integral part of the East African Rift System and has an average elevation of approximately 1,000 m. Its location coincides with a negative Bouguer gravity anomaly with a semi-circular shape, closely related to a mantle plume, which influences the Cenozoic crustal development since its impingement in Eocene-Oligocene time. The uplift of the East African Plateau, preceding volcanism, and rifting formed an important orographic barrier and tectonically controlled environment, which is profoundly influenced by climate driven processes. Its location within the equatorial realm supports recently proposed hypotheses, that topographic changes in this region must be considered as the dominant forcing factor influencing atmospheric circulation patterns and rainfall distribution. The uplift of this region has therefore often been associated with fundamental climatic and environmental changes in East Africa and adjacent regions. While the far-reaching influence of the plateau uplift is widely accepted, the timing and the magnitude of the uplift are ambiguous and are still subject to ongoing discussion. This dilemma stems from the lack of datable, geomorphically meaningful reference horizons that could record surface uplift. In order to quantify the amount of plateau uplift and to find evidence for the existence of significant relief along the East African Plateau prior to rifting, I analyzed and modeled one of the longest terrestrial lava flows; the 300-km-long Yatta phonolite flow in Kenya. This lava flow is 13.5 Ma old and originated in the region that now corresponds to the eastern rift shoulders. The phonolitic flow utilized an old riverbed that once drained the eastern flank of the plateau. Due to differential erosion this lava flow now forms a positive relief above the parallel-flowing Athi River, which is mimicking the course of the paleo-river. My approach is a lava-flow modeling, based on an improved composition and temperature dependent method to parameterize the flow of an arbitrary lava in a rectangular-shaped channel. The essential growth pattern is described by a one-dimensional model, in which Newtonian rheological flow advance is governed by the development of viscosity and/or velocity in the internal parts of the lava-flow front. Comparing assessments of different magma compositions reveal that length-dominated, channelized lava flows are characterized by high effusion rates, rapid emplacement under approximately isothermal conditions, and laminar flow. By integrating the Yatta lava flow dimensions and the covered paleo-topography (slope angle) into the model, I was able to determine the pre-rift topography of the East African Plateau. The modeling results yield a pre-rift slope of at least 0.2°, suggesting that the lava flow must have originated at a minimum elevation of 1,400 m. Hence, high topography in the region of the present-day Kenya Rift must have existed by at least 13.5 Ma. This inferred mid-Miocene uplift coincides with the two-step expansion of grasslands, as well as important radiation and speciation events in tropical Africa. Accordingly, the combination of my results regarding the Yatta lava flow emplacement history, its location, and its morphologic character, validates it as a suitable “paleo-tiltmeter” and has thus to be considered as an important topographic and volcanic feature for the topographic evolution in East Africa.
This Thesis puts its focus on the physics of neutron stars and its description with methods of numerical relativity. In the first step, a new numerical framework the Whisky2D code will be developed, which solves the relativistic equations of hydrodynamics in axisymmetry. Therefore we consider an improved formulation of the conserved form of these equations. The second part will use the new code to investigate the critical behaviour of two colliding neutron stars. Considering the analogy to phase transitions in statistical physics, we will investigate the evolution of the entropy of the neutron stars during the whole process. A better understanding of the evolution of thermodynamical quantities, like the entropy in critical process, should provide deeper understanding of thermodynamics in relativity. More specifically, we have written the Whisky2D code, which solves the general-relativistic hydrodynamics equations in a flux-conservative form and in cylindrical coordinates. This of course brings in 1/r singular terms, where r is the radial cylindrical coordinate, which must be dealt with appropriately. In the above-referenced works, the flux operator is expanded and the 1/r terms, not containing derivatives, are moved to the right-hand-side of the equation (the source term), so that the left hand side assumes a form identical to the one of the three-dimensional (3D) Cartesian formulation. We call this the standard formulation. Another possibility is not to split the flux operator and to redefine the conserved variables, via a multiplication by r. We call this the new formulation. The new equations are solved with the same methods as in the Cartesian case. From a mathematical point of view, one would not expect differences between the two ways of writing the differential operator, but, of course, a difference is present at the numerical level. Our tests show that the new formulation yields results with a global truncation error which is one or more orders of magnitude smaller than those of alternative and commonly used formulations. The second part of the Thesis uses the new code for investigations of critical phenomena in general relativity. In particular, we consider the head-on-collision of two neutron stars in a region of the parameter space where two final states a new stable neutron star or a black hole, lay close to each other. In 1993, Choptuik considered one-parameter families of solutions, S[P], of the Einstein-Klein-Gordon equations for a massless scalar field in spherical symmetry, such that for every P > P⋆, S[P] contains a black hole and for every P < P⋆, S[P] is a solution not containing singularities. He studied numerically the behavior of S[P] as P → P⋆ and found that the critical solution, S[P⋆], is universal, in the sense that it is approached by all nearly-critical solutions regardless of the particular family of initial data considered. All these phenomena have the common property that, as P approaches P⋆, S[P] approaches a universal solution S[P⋆] and that all the physical quantities of S[P] depend only on |P − P⋆|. The first study of critical phenomena concerning the head-on collision of NSs was carried out by Jin and Suen in 2007. In particular, they considered a series of families of equal-mass NSs, modeled with an ideal-gas EOS, boosted towards each other and varied the mass of the stars, their separation, velocity and the polytropic index in the EOS. In this way they could observe a critical phenomenon of type I near the threshold of black-hole formation, with the putative solution being a nonlinearly oscillating star. In a successive work, they performed similar simulations but considering the head-on collision of Gaussian distributions of matter. Also in this case they found the appearance of type-I critical behaviour, but also performed a perturbative analysis of the initial distributions of matter and of the merged object. Because of the considerable difference found in the eigenfrequencies in the two cases, they concluded that the critical solution does not represent a system near equilibrium and in particular not a perturbed Tolmann-Oppenheimer-Volkoff (TOV) solution. In this Thesis we study the dynamics of the head-on collision of two equal-mass NSs using a setup which is as similar as possible to the one considered above. While we confirm that the merged object exhibits a type-I critical behaviour, we also argue against the conclusion that the critical solution cannot be described in terms of equilibrium solution. Indeed, we show that, in analogy with what is found in, the critical solution is effectively a perturbed unstable solution of the TOV equations. Our analysis also considers fine-structure of the scaling relation of type-I critical phenomena and we show that it exhibits oscillations in a similar way to the one studied in the context of scalar-field critical collapse.
In this work, the development of a new molecular building block, based on synthetic peptides derived from decorin, is presented. These peptides represent a promising basis for the design of polymer-based biomaterials that mimic the ECM on a molecular level and exploit specific biological recognition for technical applications. Multiple sequence alignments of the internal repeats of decorin that formed the inner and outer surface of the arch-shaped protein were used to develop consensus sequences. These sequences contained conserved sequence motifs that are likely to be related to structural and functional features of the protein. Peptides representative for the consensus sequences were synthesized by microwave-assisted solid phase peptide synthesis and purified by RP-HPLC, with purities higher than 95 mol%. After confirming the desired masses by MALDI-TOF-MS, the primary structure of each peptide was investigated by 1H and 2D NMR, from which a full assignment of the chemical shifts was obtained. The characterization of the peptides conformation in solution was performed by CD spectroscopy, which demonstrated that using TFE, the peptides from the outer surface of decorin show a high propensity to fold into helical structures as observed in the original protein. To the contrary, the peptides from the inner surface did not show propensity to form stable secondary structure. The investigation of the binding capability of the peptides to Collagen I was performed by surface plasmon resonance analyses, from which all but one of the peptides representing the inner surface of decorin showed binding affinity to collagen with values of dissociation constant between 2•10-7 M and 2.3•10-4 M. On the other hand, the peptides representative for the outer surface of decorin did not show any significant interaction to collagen. This information was then used to develop experimental demonstration for the binding capabilities of the peptides from the inner surface of decorin to collagen even when used in more complicated situations close to possible appications. With this purpose, the peptide (LRELHLNNN) which showed the highest binding affinity to collagen (2•10-7 M) was functionalized with an N-terminal triple bond in order to obtain a peptide dimer via copper(I)-catalyzed cycloaddition reaction with 4,4'-diazidostilbene-2,2'-disulfonic acid. Rheological measurements showed that the presence of the peptide dimer was able to enhance the elastic modulus (G') of a collagen gel from ~ 600 Pa (collagen alone) to ~ 2700 Pa (collagen and peptide dimer). Moreover, it was shown that the mechanical properties of a collagen gel can be tailored by using different molar ratios of peptide dimer respect to collagen. The same peptide, functionalized with the triple bond, was used to obtain a peptide-dye conjugate by coupling it with N-(5'-azidopentanoyl)-5-aminofluorescein. An aqueous solution (5 vol% methanol) of the peptide dye conjugate was injected into a collagen and a hyaluronic acid (HA) gel and images of fluorescence detection showed that the diffusion of the peptide was slower in the collagen gel compared to the HA gel. The third experimental demonstration was gained using the peptide (LSELRLHNN) which showed the lower binding affinity (2.3•10-4 M) to collagen. This peptide was grafted to hyaluronic acid via EDC-chemistry, with a degree of functionalization of 7 ± 2 mol% as calculated by 1H-NMR. The grafting was further confirmed by FTIR and TGA measurements, which showed that the onset of decomposition for the HA-g-peptide decreased by 10 °C compared to the native HA. Rheological measurements showed that the elastic modulus of a system based on collagen and HA-g-peptide increased by almost two order of magnitude (G' = 200 Pa) compared to a system based on collagen and HA (G' = 0.9 Pa). Overall, this study showed that the synthetic peptides, which were identified from decorin, can be applied as potential building blocks for biomimetic materials that function via biological recognition.
The inspiral and merger of two black holes is among the most exciting and extreme events in our universe. Being one of the loudest sources of gravitational waves, they provide a unique dynamical probe of strong-field general relativity and a fertile ground for the observation of fundamental physics. While the detection of gravitational waves alone will allow us to observe our universe through an entirely new window, combining the information obtained from both gravitational wave and electro-magnetic observations will allow us to gain even greater insight in some of the most exciting astrophysical phenomena. In addition, binary black-hole mergers serve as an intriguing tool to study the geometry of space-time itself. In this dissertation we study the merger process of binary black-holes in a variety of conditions. Our results show that asymmetries in the curvature distribution on the common apparent horizon are correlated to the linear momentum acquired by the merger remnant. We propose useful tools for the analysis of black holes in the dynamical and isolated horizon frameworks and shed light on how the final merger of apparent horizons proceeds after a common horizon has already formed. We connect mathematical theorems with data obtained from numerical simulations and provide a first glimpse on the behavior of these surfaces in situations not accessible to analytical tools. We study electro-magnetic counterparts of super-massive binary black-hole mergers with fully 3D general relativistic simulations of binary black-holes immersed both in a uniform magnetic field in vacuum and in a tenuous plasma. We find that while a direct detection of merger signatures with current electro-magnetic telescopes is unlikely, secondary emission, either by altering the accretion rate of the circumbinary disk or by synchrotron radiation from accelerated charges, may be detectable. We propose a novel approach to measure the electro-magnetic radiation in these simulations and find a non-collimated emission that dominates over the collimated one appearing in the form of dual jets associated with each of the black holes. Finally, we provide an optimized gravitational wave detection pipeline using phenomenological waveforms for signals from compact binary coalescence and show that by including spin effects in the waveform templates, the detection efficiency is drastically improved as well as the bias on recovered source parameters reduced. On the whole, this disseration provides evidence that a multi-messenger approach to binary black-hole merger observations provides an exciting prospect to understand these sources and, ultimately, our universe.
The Arctic is a particularly sensitive area with respect to climate change due to the high surface albedo of snow and ice and the extreme radiative conditions. Clouds and aerosols as parts of the Arctic atmosphere play an important role in the radiation budget, which is, as yet, poorly quantified and understood. The LIDAR (Light Detection And Ranging) measurements presented in this PhD thesis contribute with continuous altitude resolved aerosol profiles to the understanding of occurrence and characteristics of aerosol layers above Ny-Ålesund, Spitsbergen. The attention was turned to the analysis of periods with high aerosol load. As the Arctic spring troposphere exhibits maximum aerosol optical depths (AODs) each year, March and April of both the years 2007 and 2009 were analyzed. Furthermore, stratospheric aerosol layers of volcanic origin were analyzed for several months, subsequently to the eruptions of the Kasatochi and Sarychev volcanoes in summer 2008 and 2009, respectively. The Koldewey Aerosol Raman LIDAR (KARL) is an instrument for the active remote sensing of atmospheric parameters using pulsed laser radiation. It is operated at the AWIPEV research base and was fundamentally upgraded within the framework of this PhD project. It is now equipped with a new telescope mirror and new detection optics, which facilitate atmospheric profiling from 450m above sea level up to the mid-stratosphere. KARL provides highly resolved profiles of the scattering characteristics of aerosol and cloud particles (backscattering, extinction and depolarization) as well as water vapor profiles within the lower troposphere. Combination of KARL data with data from other instruments on site, namely radiosondes, sun photometer, Micro Pulse LIDAR, and tethersonde system, resulted in a comprehensive data set of scattering phenomena in the Arctic atmosphere. The two spring periods March and April 2007 and 2009 were at first analyzed based on meteorological parameters, like local temperature and relative humidity profiles as well as large scale pressure patterns and air mass origin regions. Here, it was not possible to find a clear correlation between enhanced AOD and air mass origin. However, in a comparison of two cloud free periods in March 2007 and April 2009, large AOD values in 2009 coincided with air mass transport through the central Arctic. This suggests the occurrence of aerosol transformation processes during the aerosol transport to Ny-Ålesund. Measurements on 4 April 2009 revealed maximum AOD values of up to 0.12 and aerosol size distributions changing with altitude. This and other performed case studies suggest the differentiation between three aerosol event types and their origin: Vertically limited aerosol layers in dry air, highly variable hygroscopic boundary layer aerosols and enhanced aerosol load across wide portions of the troposphere. For the spring period 2007, the available KARL data were statistically analyzed using a characterization scheme, which is based on optical characteristics of the scattering particles. The scheme was validated using several case studies. Volcanic eruptions in the northern hemisphere in August 2008 and June 2009 arose the opportunity to analyze volcanic aerosol layers within the stratosphere. The rate of stratospheric AOD change was similar within both years with maximum values above 0.1 about three to five weeks after the respective eruption. In both years, the stratospheric AOD persisted at higher rates than usual until the measurements were stopped in late September due to technical reasons. In 2008, up to three aerosol layers were detected, the layer structure in 2009 was characterized by up to six distinct and thin layers which smeared out to one broad layer after about two months. The lowermost aerosol layer was continuously detected at the tropopause altitude. Three case studies were performed, all revealed rather large indices of refraction of m = (1.53–1.55) - 0.02i, suggesting the presence of an absorbing carbonaceous component. The particle radius, derived with inversion calculations, was also similar in both years with values ranging from 0.16 to 0.19 μm. However, in 2009, a second mode in the size distribution was detected at about 0.5 μm. The long term measurements with the Koldewey Aerosol Raman LIDAR in Ny-Ålesund provide the opportunity to study Arctic aerosols in the troposphere and the stratosphere not only in case studies but on longer time scales. In this PhD thesis, both, tropospheric aerosols in the Arctic spring and stratospheric aerosols following volcanic eruptions have been described qualitatively and quantitatively. Case studies and comparative studies with data of other instruments on site allowed for the analysis of microphysical aerosol characteristics and their temporal evolution.
In the present work synchronization phenomena in complex dynamical systems exhibiting multiple time scales have been analyzed. Multiple time scales can be active in different manners. Three different systems have been analyzed with different methods from data analysis. The first system studied is a large heterogenous network of bursting neurons, that is a system with two predominant time scales, the fast firing of action potentials (spikes) and the burst of repetitive spikes followed by a quiescent phase. This system has been integrated numerically and analyzed with methods based on recurrence in phase space. An interesting result are the different transitions to synchrony found in the two distinct time scales. Moreover, an anomalous synchronization effect can be observed in the fast time scale, i.e. there is range of the coupling strength where desynchronization occurs. The second system analyzed, numerically as well as experimentally, is a pair of coupled CO₂ lasers in a chaotic bursting regime. This system is interesting due to its similarity with epidemic models. We explain the bursts by different time scales generated from unstable periodic orbits embedded in the chaotic attractor and perform a synchronization analysis of these different orbits utilizing the continuous wavelet transform. We find a diverse route to synchrony of these different observed time scales. The last system studied is a small network motif of limit cycle oscillators. Precisely, we have studied a hub motif, which serves as elementary building block for scale-free networks, a type of network found in many real world applications. These hubs are of special importance for communication and information transfer in complex networks. Here, a detailed study on the mechanism of synchronization in oscillatory networks with a broad frequency distribution has been carried out. In particular, we find a remote synchronization of nodes in the network which are not directly coupled. We also explain the responsible mechanism and its limitations and constraints. Further we derive an analytic expression for it and show that information transmission in pure phase oscillators, such as the Kuramoto type, is limited. In addition to the numerical and analytic analysis an experiment consisting of electrical circuits has been designed. The obtained results confirm the former findings.
Public debate about energy relations between the EU and Russia is distorted. These distortions present considerable obstacles to the development of true partnership. At the core of the conflict is a struggle for resource rents between energy producing, energy consuming and transit countries. Supposed secondary aspects, however, are also of great importance. They comprise of geopolitics, market access, economic development and state sovereignty. The European Union, having engaged in energy market liberalisation, faces a widening gap between declining domestic resources and continuously growing energy demand. Diverse interests inside the EU prevent the definition of a coherent and respected energy policy. Russia, for its part, is no longer willing to subsidise its neighbouring economies by cheap energy exports. The Russian government engages in assertive policies pursuing Russian interests. In so far, it opts for a different globalisation approach, refusing the role of mere energy exporter. In view of the intensifying struggle for global resources, Russia, with its large energy potential, appears to be a very favourable option for European energy supplies, if not the best one. However, several outcomes of the strategic game between the two partners can be imagined. Engaging in non-cooperative strategies will in the end leave all stakeholders worse-off. The European Union should therefore concentrate on securing its partnership with Russia instead of damaging it. Stable cooperation would need the acceptance that the partner may pursue his own goals, which might be different from one’s own interests. The question is, how can a sustainable compromise be found? This thesis finds that a mix of continued dialogue, a tit for tat approach bolstered by an international institutional framework and increased integration efforts appears as a preferable solution.
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.
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.
Functional analyses of microtubule and centrosome-associated proteins in Dictyostelium discoideum
(2011)
Understanding the role of microtubule-associated proteins is the key to understand the complex mechanisms regulating microtubule dynamics. This study employs the model system Dictyostelium discoideum to elucidate the role of the microtubule-associated protein TACC (Transforming acidic coiled-coil) in promoting microtubule growth and stability. Dictyostelium TACC was localized at the centrosome throughout the entire cell cycle. The protein was also detected at microtubule plus ends, however, unexpectedly only during interphase but not during mitosis. The same cell cycle-dependent localization pattern was observed for CP224, the Dictyostelium XMAP215 homologue. These ubiquitous MAPs have been found to interact with TACC proteins directly and are known to act as microtubule polymerases and nucleators. This work shows for the first time in vivo that both a TACC and XMAP215 family protein can differentially localize to microtubule plus ends during interphase and mitosis. RNAi knockdown mutants revealed that TACC promotes microtubule growth during interphase and is essential for proper formation of astral microtubules in mitosis. In many organisms, impaired microtubule stability upon TACC depletion was explained by the failure to efficiently recruit the TACC-binding XMAP215 protein to centrosomes or spindle poles. By contrast, fluorescence recovery after photobleaching (FRAP) analyses conducted in this study demonstrate that in Dictyostelium recruitment of CP224 to centrosomes or spindle poles is not perturbed in the absence of TACC. Instead, CP224 could no longer be detected at the tips of microtubules in TACC mutant cells. This finding demonstrates for the first time in vivo that a TACC protein is essential for the association of an XMAP215 protein with microtubule plus ends. The GFP-TACC strains generated in this work also turned out to be a valuable tool to study the unusual microtubule dynamics in Dictyostelium. Here, microtubules exhibit a high degree of lateral bending movements but, in contrast most other organisms, they do not obviously undergo any growth or shrinkage events during interphase. Despite of that they are affected by microtubuledepolymerizing drugs such as thiabendazole or nocodazol which are thought to act solely on dynamic microtubules. Employing 5D-fluorescence live cell microscopy and FRAP analyses this study suggests Dictyostelium microtubules to be dynamic only in the periphery, while they are stable at the centrosome. In the recent years, the identification of yet unknown components of the Dictyostelium centrosome has made tremendous progress. A proteomic approach previously conducted by our group disclosed several uncharacterized candidate proteins, which remained to be verified as genuine centrosomal components. The second part of this study focuses on the investigation of three such candidate proteins, Cenp68, CP103 and the putative spindle assembly checkpoint protein Mad1. While a GFP-CP103 fusion protein could clearly be localized to isolated centrosomes that are free of microtubules, Cenp68 and Mad1 were found to associate with the centromeres and kinetochores, respectively. The investigation of Cenp68 included the generation of a polyclonal anti-Cenp68 antibody, the screening for interacting proteins and the generation of knockout mutants which, however, did not display any obvious phenotype. Yet, Cenp68 has turned out as a very useful marker to study centromere dynamics during the entire cell cycle. During mitosis, GFP-Mad1 localization strongly resembled the behavior of other Mad1 proteins, suggesting the existence of a yet uncharacterized spindle assembly checkpoint in Dictyostelium.
Plant growth and survival depend on photosynthesis in the leaves. This involves the uptake of carbon dioxide from the atmosphere and the simultaneous capture of light energy to produce organic molecules, which enter metabolism and are converted to many other compounds which then serve as building blocks for biomass growth. Leaves are organs specialised for photosynthetic carbon dioxide fixation. The function of leaves involves many trade-offs which must be optimised in order to achieve effective use of resources and maximum photosynthesis. It is known that the morphology of leaves adjusts to the growth environment of plants and this is important for optimising their function for photosynthesis. However, it is unclear how this adjustment is regulated. The general aim of the work presented in this thesis is to understand how leaf growth and morphology are regulated in the model species Arabidopsis thaliana. Special attention was dedicated to the possibility that there might be internal metabolic signals within the plant which affect the growth and development of leaves. In order to investigate this question, leaf growth and development must be considered beyond the level of the single organ and in the context of the whole plant because leaves do not grow autonomously but depend on resources and regulatory influences delivered by the rest of the plant. Due to the complexity of this question, three complementary approaches were taken. In the first and most specific approach it was asked whether a proposed down-stream component of sucrose signalling, trehalose-6-phosphate (Tre-6-P), might influence leaf development and growth. To investigate this question, transgenic Arabidopsis lines with perturbed levels of Tre-6-P were generated using the constitutive 35S promoter to express bacterial enzymes involved in trehalose metabolism. These experiments also led to an unanticipated project concerning a possible role for Tre-6-P in stomatal function, which is another very important function in leaves. In a second and more general approach it was investigated whether changes in sugar levels in plants affect the morphogenesis of leaves in response to light. For this, a series of metabolic mutants impaired in central metabolism were grown in one light environment and their leaf morphology was analysed. In a third and even more general approach the natural variation in leaf and rosette morphological traits was investigated in a panel of wild Arabidopsis accessions with the aim of understanding how leaf morphology affects leaf function and whole plant growth and how different traits relate to each other. The analysis included measurements of leaf morphological traits as well as the number of leaves in the plant to put leaf morphology in a whole plant context. The variance in plant growth could not be explained by variation in photosynthetic rates and only to a small degree by variation in rates of dark respiration. There were four key axes of variation in rosette and leaf morphology – leaf area growth, leaf thickness, cell expansion and leaf number. These four processes were integrated in the context of whole plant growth by models that employed a multiple linear regression approach. This then led to a theoretical approach in which a simple allometric mathematical model was constructed, linking leaf number, leaf size and plant growth rate together in a whole plant context in Arabidopsis.
Regulation of gene transcription plays a major role in mediating cellular responses and physiological behavior in all known organisms. The finding that similar genes are often regulated in a similar manner (co-regulated or "co-expressed") has directed several "guilt-by-association" approaches in order to reverse-engineer the cellular transcriptional networks using gene expression data as a compass. This kind of studies has been considerably assisted in the recent years by the development of high-throughput transcript measurement platforms, specifically gene microarrays and next-generation sequencing. In this thesis, I describe several approaches for improving the extraction and interpretation of the information contained in microarray based gene expression data, through four steps: (1) microarray platform design, (2) microarray data normalization, (3) gene network reverse engineering based on expression data and (4) experimental validation of expression-based guilt-by-association inferences. In the first part test case is shown aimed at the generation of a microarray for Thellungiella salsuginea, a salt and drought resistant close relative to the model plant Arabidopsis thaliana; the transcripts of this organism are generated on the combination of publicly available ESTs and newly generated ad-hoc next-generation sequencing data. Since the design of a microarray platform requires the availability of highly reliable and non-redundant transcript models, these issues are addressed consecutively, proposing several different technical solutions. In the second part I describe how inter-array correlation artifacts are generated by the common microarray normalization methods RMA and GCRMA, together with the technical and mathematical characteristics underlying the problem. A solution is proposed in the form of a novel normalization method, called tRMA. The third part of the thesis deals with the field of expression-based gene network reverse engineering. It is shown how different centrality measures in reverse engineered gene networks can be used to distinguish specific classes of genes, in particular essential genes in Arabidopsis thaliana, and how the use of conditional correlation can add a layer of understanding over the information flow processes underlying transcript regulation. Furthermore, several network reverse engineering approaches are compared, with a particular focus on the LASSO, a linear regression derivative rarely applied before in global gene network reconstruction, despite its theoretical advantages in robustness and interpretability over more standard methods. The performance of LASSO is assessed through several in silico analyses dealing with the reliability of the inferred gene networks. In the final part, LASSO and other reverse engineering methods are used to experimentally identify novel genes involved in two independent scenarios: the seed coat mucilage pathway in Arabidopsis thaliana and the hypoxic tuber development in Solanum tuberosum. In both cases an interesting method complementarity is shown, which strongly suggests a general use of hybrid approaches for transcript expression-based inferences. In conclusion, this work has helped to improve our understanding of gene transcription regulation through a better interpretation of high-throughput expression data. Part of the network reverse engineering methods described in this thesis have been included in a tool (CorTo) for gene network reverse engineering and annotated visualization from custom transcription datasets.
Most of the microelectronic circuits fabricated today are synchronous, i.e. they are driven by one or several clock signals. Synchronous circuit design faces several fundamental challenges such as high-speed clock distribution, integration of multiple cores operating at different clock rates, reduction of power consumption and dealing with voltage, temperature, manufacturing and runtime variations. Asynchronous or clockless design plays a key role in alleviating these challenges, however the design and test of asynchronous circuits is much more difficult in comparison to their synchronous counterparts. A driving force for a widespread use of asynchronous technology is the availability of mature EDA (Electronic Design Automation) tools which provide an entire automated design flow starting from an HDL (Hardware Description Language) specification yielding the final circuit layout. Even though there was much progress in developing such EDA tools for asynchronous circuit design during the last two decades, the maturity level as well as the acceptance of them is still not comparable with tools for synchronous circuit design. In particular, logic synthesis (which implies the application of Boolean minimisation techniques) for the entire system's control path can significantly improve the efficiency of the resulting asynchronous implementation, e.g. in terms of chip area and performance. However, logic synthesis, in particular for asynchronous circuits, suffers from complexity problems. Signal Transitions Graphs (STGs) are labelled Petri nets which are a widely used to specify the interface behaviour of speed independent (SI) circuits - a robust subclass of asynchronous circuits. STG decomposition is a promising approach to tackle complexity problems like state space explosion in logic synthesis of SI circuits. The (structural) decomposition of STGs is guided by a partition of the output signals and generates a usually much smaller component STG for each partition member, i.e. a component STG with a much smaller state space than the initial specification. However, decomposition can result in component STGs that in isolation have so-called irreducible CSC conflicts (i.e. these components are not SI synthesisable anymore) even if the specification has none of them. A new approach is presented to avoid such conflicts by introducing internal communication between the components. So far, STG decompositions are guided by the finest output partitions, i.e. one output per component. However, this might not yield optimal circuit implementations. Efficient heuristics are presented to determine coarser partitions leading to improved circuits in terms of chip area. For the new algorithms correctness proofs are given and their implementations are incorporated into the decomposition tool DESIJ. The presented techniques are successfully applied to some benchmarks - including 'real-life' specifications arising in the context of control resynthesis - which delivered promising results.
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.
The present thesis was born and evolved within the RAdial Velocity Experiment (RAVE) with the goal of measuring chemical abundances from the RAVE spectra and exploit them to investigate the chemical gradients along the plane of the Galaxy to provide constraints on possible Galactic formation scenarios. RAVE is a large spectroscopic survey which aims to observe spectroscopically ~10^6 stars by the end of 2012 and measures their radial velocities, atmospheric parameters and chemical abundances. The project makes use of the UK Schmidt telescope at Australian Astronomical Observatory (AAO) in Siding Spring, Australia, equipped with the multiobject spectrograph 6dF. To date, RAVE collected and measured more than 450,000 spectra. The precision of the chemical abundance estimations depends on the reliability of the atomic and atmosphere parameters adopted (in particular the oscillator strengths of the absorption lines and the effective temperature, gravity, and metallicity of the stars measured). Therefore we first identified 604 absorption lines in the RAVE wavelength range and refined their oscillator strengths with an inverse spectral analysis. Then, we improved the RAVE stellar parameters by modifying the RAVE pipeline and the spectral library the pipeline rely on. The modifications removed some systematic errors in stellar parameters discovered during this work. To obtain chemical abundances, we developed two different processing pipelines. Both of them perform chemical abundances measurements by assuming stellar atmospheres in Local Thermodynamic Equilibrium (LTE). The first one determines elements abundances from equivalent widths of absorption lines. Since this pipeline showed poor sensibility on abundances relative to iron, it has been superseded. The second one exploits the chi^2 minimization technique between observed and model spectra. Thanks to its precision, it has been adopted for the creation of the RAVE chemical catalogue. This pipeline provides abundances with uncertains of about ~0.2dex for spectra with signal-to-noise ratio S/N>40 and ~0.3dex for spectra with 20>S/N>40. For this work, the pipeline measured chemical abundances up to 7 elements for 217,358 RAVE stars. With these data we investigated the chemical gradients along the Galactic radius of the Milky Way. We found that stars with low vertical velocities |W| (which stay close to the Galactic plane) show an iron abundance gradient in agreement with previous works (~-0.07$ dex kpc^-1) whereas stars with larger |W| which are able to reach larger heights above the Galactic plane, show progressively flatter gradients. The gradients of the other elements follow the same trend. This suggests that an efficient radial mixing acts in the Galaxy or that the thick disk formed from homogeneous interstellar matter. In particular, we found hundreds of stars which can be kinetically classified as thick disk stars exhibiting a chemical composition typical of the thin disk. A few stars of this kind have already been detected by other authors, and their origin is still not clear. One possibility is that they are thin disk stars kinematically heated, and then underwent an efficient radial mixing process which blurred (and so flattened) the gradient. Alternatively they may be a transition population" which represents an evolutionary bridge between thin and thick disk. Our analysis shows that the two explanations are not mutually exclusive. Future follow-up high resolution spectroscopic observations will clarify their role in the Galactic disk evolution.
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”.
In this thesis chemical reactions under hydrothermal conditions were explored, whereby emphasis was put on green chemistry. Water at high temperature and pressure acts as a benign solvent. Motivation to work under hydrothermal conditions was well-founded in the tunability of physicochemical properties with temperature, e.g. of dielectric constant, density or ion product, which often resulted in surprising reactivity. Another cornerstone was the implementation of the principles of green chemistry. Besides the use of water as solvent, this included the employment of a sustainable feedstock and the sensible use of resources by minimizing waste and harmful intermediates and additives. To evaluate the feasibility of hydrothermal conditions for chemical synthesis, exemplary reactions were performed. These were carried out in a continuous flow reactor, allowing for precise control of reaction conditions and kinetics measurements. In most experiments a temperature of 200 °C in combination with a pressure of 100 bar was chosen. In some cases the temperature was even raised to 300 °C. Water in this subcritical range can also be found in nature at hydrothermal vents on the ocean floor. On the primitive earth, environments with such conditions were however present in larger numbers. Therefore we tested whether biologically important carbohydrates could be formed at high temperature from the simple, probably prebiotic precursor formaldehyde. Indeed, this formose reaction could be carried out successfully, although the yield was lower compared to the counterpart reaction under ambient conditions. However, striking differences regarding selectivity and necessary catalysts were observed. At moderate temperatures bases and catalytically active cations like Ca2+ are necessary and the main products are hexoses and pentoses, which accumulate due to their higher stability. In contrast, in high-temperature water no catalyst was necessary but a slightly alkaline solution was sufficient. Hexoses were only formed in negligible amounts, whereas pentoses and the shorter carbohydrates accounted for the major fraction. Amongst the pentoses there was some preference for the formation of ribose. Even deoxy sugars could be detected in traces. The observation that catalysts can be avoided was successfully transferred to another reaction. In a green chemistry approach platform chemicals must be produced from sustainable resources. Carbohydrates can for instance be employed as a basis. They can be transformed to levulinic acid and formic acid, which can both react via a transfer hydrogenation to the green solvent and biofuel gamma-valerolactone. This second reaction usually requires catalysis by Ru or Pd, which are neither sustainable nor low-priced. Under hydrothermal conditions these heavy metals could be avoided and replaced by cheap salts, taking advantage of the temperature dependence of the acid dissociation constant. Simple sulfate was recognized as a temperature switchable base. With this additive high yield could be achieved by simultaneous prevention of waste. In contrast to conventional bases, which create salt upon neutralization, a temperature switchable base becomes neutral again when cooled down and thus can be reused. This adds another sustainable feature to the high atom economy of the presented hydrothermal synthesis. In a last study complex decomposition pathways of biomass were investigated. Gas chromatography in conjunction with mass spectroscopy has proven to be a powerful tool for the identification of unknowns. It was observed that several acids were formed when carbohydrates were treated with bases at high temperature. This procedure was also applied to digest wood. Afterwards it was possible to fermentate the solution and a good yield of methane was obtained. This has to be regarded in the light of the fact that wood practically cannot be used as a feedstock in a biogas factory. Thus the hydrothermal pretreatment is an efficient means to employ such materials as well. Also the reaction network of the hydrothermal decomposition of glycine was investigated using isotope-labeled compounds as comparison for the unambiguous identification of unknowns. This refined analysis allowed the identification of several new molecules and pathways, not yet described in literature. In summary several advantages could be taken from synthesis in high-temperature water. Many catalysts, absolutely necessary under ambient conditions, could either be completely avoided or replaced by cheap, sustainable alternatives. In this respect water is not only a green solvent, but helps to prevent waste and preserves resources.
Nanoporous carbon materials are widely used in industry as adsorbents or catalyst supports, whilst becoming increasingly critical to the developing fields of energy storage / generation or separation technologies. In this thesis, the combined use of carbohydrate hydrothermal carbonisation (HTC) and templating strategies is demonstrated as an efficient route to nanostructured carbonaceous materials. HTC is an aqueous-phase, low-temperature (e.g. 130 – 200 °C) carbonisation, which proceeds via dehydration / poly-condensation of carbon precursors (e.g. carbohydrates and their derivatives), allowing facile access to highly functional carbonaceous materials. Whilst possessing utile, modifiable surface functional groups (e.g. -OH and -C=O-containing moieties), materials synthesised via HTC typically present limited accessible surface area or pore volume. Therefore, this thesis focuses on the development of fabrication routes to HTC materials which present enhanced textural properties and well-defined porosity. In the first discussed synthesis, a combined hard templating / HTC route was investigated using a range of sacrificial inorganic templates (e.g. mesoporous silica beads and macroporous alumina membranes (AAO)). Via pore impregnation of mesoporous silica beads with a biomass-derived carbon source (e.g. 2-furaldehyde) and subsequent HTC at 180 oC, an inorganic / carbonaceous hybrid material was produced. Removal of the template component by acid etching revealed the replication of the silica into mesoporous carbonaceous spheres (particle size ~ 5 μm), representing the inverse morphological structure of the original inorganic body. Surface analysis (e.g. FTIR) indicated a material decorated with hydrophilic (oxygenated) functional groups. Further thermal treatment at increasingly elevated temperatures (e.g. at 350, 550, 750 oC) under inert atmosphere allowed manipulation of functionalities from polar hydrophilic to increasingly non-polar / hydrophobic structural motifs (e.g. extension of the aromatic / pseudo-graphitic nature), thus demonstrating a process capable of simultaneous control of nanostructure and surface / bulk chemistry. As an extension of this approach, carbonaceous tubular nanostructures with controlled surface functionality were synthesised by the nanocasting of uniform, linear macropores of an AAO template (~ 200 nm). In this example, material porosity could be controlled, showing increasingly microporous tube wall features as post carbonisation temperature increased. Additionally, by taking advantage of modifiable surface groups, the introduction of useful polymeric moieties (i.e. grafting of thermoresponsive poly(N-isopropylacrylamide)) was also demonstrated, potentially enabling application of these interesting tubular structures in the fields of biotechnology (e.g. enzyme immobilization) and medicine (e.g. as drug micro-containers). Complimentary to these hard templating routes, a combined HTC / soft templating route for the direct synthesis of ordered porous carbonaceous materials was also developed. After selection of structural directing agents and optimisation of synthesis composition, the F127 triblock copolymer (i.e. ethylene oxide (EO)106 propylene oxide (PO)70 ethylene oxide (EO)106) / D-Fructose system was extensively studied. D-Fructose was found to be a useful carbon precursor as the HTC process could be performed at 130 oC, thus allowing access to stable micellular phase. Thermolytic template removal from the synthesised ordered copolymer / carbon composite yielded functional cuboctahedron single crystalline-like particles (~ 5 μm) with well ordered pore structure of a near perfect cubic Im3m symmetry. N2 sorption analysis revealed a predominantly microporous carbonaceous material (i.e. Type I isotherm, SBET = 257 m2g-1, 79 % microporosity) possessing a pore size of ca. 0.9 nm. The addition of a simple pore swelling additive (e.g. trimethylbenzene (TMB)) to this system was found to direct pore size into the mesopore size domain (i.e. Type IV isotherm, SBET = 116 m2g-1, 60 % mesoporosity) generating pore size of ca. 4 nm. It is proposed that in both cases as HTC proceeds to generate a polyfuran-like network, the organised block copolymer micellular phase is essentially “templated”, either via hydrogen bonding between hydrophilic poly(EO) moiety and the carbohydrate or via hydrophobic interaction between hydrophobic poly(PO) moiety and forming polyfuran-like network, whilst the additive TMB presumably interact with poly(PO) moieties, thus swelling the hydrophobic region expanding the micelle template size further into the mesopore range.
Towards greener stationary phases : thermoresponsive and carbonaceous chromatographic supports
(2011)
Polymers which are sensitive towards external physical, chemical and electrical stimuli are termed as ‘intelligent materials’ and are widely used in medical and engineering applications. Presently, polymers which can undergo a physical change when heat is applied at a certain temperature (cloud point) in water are well-studied for this property in areas of separation chemistry, gene and drug delivery and as surface modifiers. One example of such a polymer is the poly (N-isopropylacrylamide) PNIPAAM, where it is dissolved well in water below 32 oC, while by increasing the temperature further leads to its precipitation. In this work, an alternative polymer poly (2-(2-methoxy ethoxy)ethyl methacrylate-co- oligo(ethylene glycol) methacrylate) (P(MEO2MA-co-OEGMA)) is studied due to its biocompatibility and the ability to vary its cloud points in water. When a layer of temperature responsive polymer was attached to a single continuous porous piece of silica-based material known as a monolith, the thermoresponsive characteristic was transferred to the column surfaces. The hybrid material was demonstrated to act as a simple temperature ‘switch’ in the separation of a mixture of five steroids under water. Different analytes were observed to be separated under varying column temperatures. Furthermore, more complex biochemical compounds such as proteins were also tested for separation. The importance of this work is attributed to separation processes utilizing environmentally friendly conditions, since harsh chemical environments conventionally used to resolve biocompounds could cause their biological activities to be rendered inactive.
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.
The creation of complex polymer structures has been one of the major research topics over the last couple of decades. This work deals with the synthesis of (block co-)polymers, the creation of complex and stimuli-responsive aggregates by self-assembly, and the cross-linking of these structures. Also the higher-order self-assembly of the aggregates is investigated. The formation of poly-2-oxazoline based micelles in aqueous solution and their simultaneous functionalization and cross-linking using thiol-yne chemistry is e.g. presented. By introducing pH responsive thiols in the core of the micelles the influence of charged groups in the core of micelles on the entire structure can be studied. The charging of these groups leads to a swelling of the core and a decrease in the local concentration of the corona forming block (poly(2-ethyl-2-oxazoline)). This decrease in concentration yields a shift in the cloud point temperature to higher temperatures for this Type I thermoresponsive polymer. When the swelling of the core is prohibited, e.g. by the introduction of sufficient amounts of salt, this behavior disappears. Similar structures can be prepared using complex coacervate core micelles (C3Ms) built through the interaction of weakly acidic and basic polymer blocks. The advantage of these structures is that two different stabilizing blocks can be incorporated, which allows for more diverse and complex structures and behavior of the micelles. Using block copolymers with either a polyanionic or a polycationic block C3Ms could be created with a corona which contains two different soluble nonionic polymers, which either have a mixed corona or a Janus type corona, depending on the polymers that were chosen. Using NHS and EDC the micelles could easily be cross-linked by the formation of amide bonds in the core of the micelles. The higher-order self-assembly behavior of these core cross-linked complex coacervate core micelles (C5Ms) was studied. Due to the cross-linking the micelles are stabilized towards changes in pH and ionic strength, but polymer chains are also no longer able to rearrange. For C5Ms with a mixed corona likely network structures were formed upon the collapse of the thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm), whereas for Janus type C5Ms well defined spherical aggregates of micelles could be obtained, depending on the pH of the solution. Furthermore it could be shown that Janus micelles can adsorb onto inorganic nanoparticles such as colloidal silica (through a selective interaction between PEO and the silica surface) or gold nanoparticles (by the binding of thiol end-groups). Asymmetric aggregates were also formed using the streptavidin-biotin binding motive. This is achieved by using three out of the four binding sites of streptavidin for the binding of one three-arm star polymer, end-functionalized with biotin groups. A homopolymer with one biotin end-group can be used to occupy the last position. This binding of two different polymers makes it possible to create asymmetric complexes. This phase separation is theoretically independent of the kind of polymer since the structure of the protein is the driving force, not the intrinsic phase separation between polymers. Besides Janus structures also specific cross-linking can be achieved by using other mixing ratios.
The needs for sustainable energy generation, but also a sustainable chemistry display the basic motivation of the current thesis. By different single investigated cases, which are all related to the element carbon, the work can be devided into two major topics. At first, the sustainable synthesis of “useful” carbon materials employing the process of hydrothermal carbonisation (HC) is described. In the second part, the synthesis of heteroatom - containing carbon materials for electrochemical and fuel cell applications employing ionic liquid precursors is presented. On base of a thorough review of the literature on hydrothermolysis and hydrothermal carbonisation of sugars in addition to the chemistry of hydroxymethylfurfural, mechanistic considerations of the formation of hydrothermal carbon are proposed. On the base of these reaction schemes, the mineral borax, is introduced as an additive for the hydrothermal carbonisation of glucose. It was found to be a highly active catalyst, resulting in decreased reaction times and increased carbon yields. The chemical impact of borax, in the following is exploited for the modification of the micro- and nanostructure of hydrothermal carbon. From the borax - mediated aggregation of those primary species, widely applicable, low density, pure hydrothermal carbon aerogels with high porosities and specific surface areas are produced. To conclude the first section of the thesis, a short series of experiments is carried out, for the purpose of demonstrating the applicability of the HC model to “real” biowaste i.e. watermelon waste as feedstock for the production of useful materials. In part two cyano - containing ionic liquids are employed as precursors for the synthesis of high - performance, heteroatom - containing carbon materials. By varying the ionic liquid precursor and the carbonisation conditions, it was possible to design highly active non - metal electrocatalyst for the reduction of oxygen. In the direct reduction of oxygen to water (like used in polymer electrolyte fuel cells), compared to commercial platinum catalysts, astonishing activities are observed. In another example the selective and very cost efficient electrochemical synthesis of hydrogen peroxide is presented. In a last example the synthesis of graphitic boron carbon nitrides from the ionic liquid 1 - Ethyl - 3 - methylimidazolium - tetracyanoborate is investigated in detail. Due to the employment of unreactive salts as a new tool to generate high surface area these materials were first time shown to be another class of non - precious metal oxygen reduction electrocatalyst.
Mathematical modeling of biological phenomena has experienced increasing interest since new high-throughput technologies give access to growing amounts of molecular data. These modeling approaches are especially able to test hypotheses which are not yet experimentally accessible or guide an experimental setup. One particular attempt investigates the evolutionary dynamics responsible for today's composition of organisms. Computer simulations either propose an evolutionary mechanism and thus reproduce a recent finding or rebuild an evolutionary process in order to learn about its mechanism. The quest for evolutionary fingerprints in metabolic and gene-coexpression networks is the central topic of this cumulative thesis based on four published articles. An understanding of the actual origin of life will probably remain an insoluble problem. However, one can argue that after a first simple metabolism has evolved, the further evolution of metabolism occurred in parallel with the evolution of the sequences of the catalyzing enzymes. Indications of such a coevolution can be found when correlating the change in sequence between two enzymes with their distance on the metabolic network which is obtained from the KEGG database. We observe that there exists a small but significant correlation primarily on nearest neighbors. This indicates that enzymes catalyzing subsequent reactions tend to be descended from the same precursor. Since this correlation is relatively small one can at least assume that, if new enzymes are no "genetic children" of the previous enzymes, they certainly be descended from any of the already existing ones. Following this hypothesis, we introduce a model of enzyme-pathway coevolution. By iteratively adding enzymes, this model explores the metabolic network in a manner similar to diffusion. With implementation of an Gillespie-like algorithm we are able to introduce a tunable parameter that controls the weight of sequence similarity when choosing a new enzyme. Furthermore, this method also defines a time difference between successive evolutionary innovations in terms of a new enzyme. Overall, these simulations generate putative time-courses of the evolutionary walk on the metabolic network. By a time-series analysis, we find that the acquisition of new enzymes appears in bursts which are pronounced when the influence of the sequence similarity is higher. This behavior strongly resembles punctuated equilibrium which denotes the observation that new species tend to appear in bursts as well rather than in a gradual manner. Thus, our model helps to establish a better understanding of punctuated equilibrium giving a potential description at molecular level. From the time-courses we also extract a tentative order of new enzymes, metabolites, and even organisms. The consistence of this order with previous findings provides evidence for the validity of our approach. While the sequence of a gene is actually subject to mutations, its expression profile might also indirectly change through the evolutionary events in the cellular interplay. Gene coexpression data is simply accessible by microarray experiments and commonly illustrated using coexpression networks where genes are nodes and get linked once they show a significant coexpression. Since the large number of genes makes an illustration of the entire coexpression network difficult, clustering helps to show the network on a metalevel. Various clustering techniques already exist. However, we introduce a novel one which maintains control of the cluster sizes and thus assures proper visual inspection. An application of the method on Arabidopsis thaliana reveals that genes causing a severe phenotype often show a functional uniqueness in their network vicinity. This leads to 20 genes of so far unknown phenotype which are however suggested to be essential for plant growth. Of these, six indeed provoke such a severe phenotype, shown by mutant analysis. By an inspection of the degree distribution of the A.thaliana coexpression network, we identified two characteristics. The distribution deviates from the frequently observed power-law by a sharp truncation which follows after an over-representation of highly connected nodes. For a better understanding, we developed an evolutionary model which mimics the growth of a coexpression network by gene duplication which underlies a strong selection criterion, and slight mutational changes in the expression profile. Despite the simplicity of our assumption, we can reproduce the observed properties in A.thaliana as well as in E.coli and S.cerevisiae. The over-representation of high-degree nodes could be identified with mutually well connected genes of similar functional families: zinc fingers (PF00096), flagella, and ribosomes respectively. In conclusion, these four manuscripts demonstrate the usefulness of mathematical models and statistical tools as a source of new biological insight. While the clustering approach of gene coexpression data leads to the phenotypic characterization of so far unknown genes and thus supports genome annotation, our model approaches offer explanations for observed properties of the coexpression network and furthermore substantiate punctuated equilibrium as an evolutionary process by a deeper understanding of an underlying molecular mechanism.
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.
Interaction of land surface processes and the atmophere in the Arctic - senitivities and extremes
(2011)
Regulation of potassium channels in plants : biophysical mechanisms and physiological implacations
(2011)
Tangible business process modeling : design and evaluation of a process model elicitation Technique
(2011)
Lithopheric rheology at the Dead Sea Transform Fault constrained by thermo-mechanical modeling
(2011)
Impact of apoplastic glycoside hydrolases on xyloglucan structure and function in arabidopsis
(2011)
Turning wind into power : effects of stakeholder networks on renewalbe energy governanace in India
(2011)
Business Process Management (BPM) emerged as a means to control, analyse, and optimise business operations. Conceptual models are of central importance for BPM. Most prominently, process models define the behaviour that is performed to achieve a business value. In essence, a process model is a mapping of properties of the original business process to the model, created for a purpose. Different modelling purposes, therefore, result in different models of a business process. Against this background, the misalignment of process models often observed in the field of BPM is no surprise. Even if the same business scenario is considered, models created for strategic decision making differ in content significantly from models created for process automation. Despite their differences, process models that refer to the same business process should be consistent, i.e., free of contradictions. Apparently, there is a trade-off between strictness of a notion of consistency and appropriateness of process models serving different purposes. Existing work on consistency analysis builds upon behaviour equivalences and hierarchical refinements between process models. Hence, these approaches are computationally hard and do not offer the flexibility to gradually relax consistency requirements towards a certain setting. This thesis presents a framework for the analysis of behaviour consistency that takes a fundamentally different approach. As a first step, an alignment between corresponding elements of related process models is constructed. Then, this thesis conducts behavioural analysis grounded on a relational abstraction of the behaviour of a process model, its behavioural profile. Different variants of these profiles are proposed, along with efficient computation techniques for a broad class of process models. Using behavioural profiles, consistency of an alignment between process models is judged by different notions and measures. The consistency measures are also adjusted to assess conformance of process logs that capture the observed execution of a process. Further, this thesis proposes various complementary techniques to support consistency management. It elaborates on how to implement consistent change propagation between process models, addresses the exploration of behavioural commonalities and differences, and proposes a model synthesis for behavioural profiles.
Within this work, three physicochemical methods for the hydrophobization of initially hydrophilic solid particles are investigated. The modified particles are then used for the stabilization of oil-in-water (o/w) emulsions. For all introduced methods electrostatic interactions between strongly or weakly charged groups in the system are es-sential. (i) Short chain alkylammonium bromides (C4 – C12) adsorb on oppositely charged solid particles. Macroscopic contact angle measurements of water droplets under air and hexane on flat silica surfaces in dependency of the surface charge density and alkylchain-length allow the calculation of the surface energy and give insights into the emulsification properties of solid particles modified with alkyltrimethylammonium bromides. The measure-ments show an increase of the contact angle with increasing surface charge density, due to the enhanced adsorp-tion of the oppositely charged alkylammonium bromides. Contact angles are higher for longer alkylchain lengths. The surface energy calculations show that in particular the surface-hexane or surface-air interfacial en-ergy is being lowered upon alkylammonium adsorption, while a significant increase of the surface-water interfa-cial energy occurs only at long alkyl chain lengths and high surface charge densities. (ii) The thickness and the charge density of an adsorbed weak polyelectrolyte layer (e.g. PMAA, PAH) influence the wettability of nanoparticles (e.g. alumina, silica, see Scheme 1(b)). Furthermore, the isoelectric point and the pH range of colloidal stability of particle-polyelectrolyte composites depend on the thickness of the weak polye-lectrolyte layer. Silica nanoparticles with adsorbed PAH and alumina nanoparticles with adsorbed PMAA be-come interfacially active and thus able to stabilize o/w emulsions when the degree of dissociation of the polye-lectrolyte layer is below 80 %. The average droplet size after emulsification of dodecane in water depends on the thickness and the degree of dissociation of the adsorbed PE-layer. The visualization of the particle-stabilized o/w emulsions by cryogenic SEM shows that for colloidally stable alumina-PMAA composites the oil-water interface is covered with a closely packed monolayer of particles, while for the colloidally unstable case closely packed aggregated particles deposit on the interface. (iii) By emulsifying a mixture of the corrosion inhibitor 8-hydroxyquinoline (8-HQ) and styrene with silica nanoparticles a highly stable o/w emulsion can be obtained in a narrow pH window. The amphoteric character of 8-HQ enables a pH dependent electrostatic interaction with silica nanoparticles, which can render them interfa-cially active. Depending on the concentration and the degree of dissociation of 8-HQ the adsorption onto silica results from electrostatic or aromatic interactions between 8-HQ and the particle-surface. At intermediate amounts of adsorbed 8-HQ the oil wettability of the particles becomes sufficient for stabilizing o/w emulsions. Cryogenic SEM visualization shows that the particles arrange then in a closely packed shell consisting of partly of aggregated domains on the droplet interface. For further increasing amounts of adsorbed 8-HQ the oil wet-tability is reduced again and the particles ability to stabilize emulsions decreases. By the addition of hexadecane to the oil phase the size of the droplets can be reduced down to 200 nm by in-creasing the silica mass fraction. Subsequent polymerization produces corrosion inhibitor filled (20 wt-%) poly-styrene-silica composite particles. The measurement of the release of 8-hydroxyquinoline shows a rapid increase of 8-hydroxyquinoline in a stirred aqueous solution indicating the release of the total content in less than 5 min-utes. The method is extended for the encapsulation of other organic corrosion inhibitors. The silica-polymer-inhibitor composite particles are then dispersed in a water based alkyd emulsion, and the dispersion is used to coat flat aluminium substrates. After drying and cross-linking the polmer-film Confocal Laser Scanning Micros-copy is employed revealing a homogeneous distribution of the particles in the film. Electrochemical Impedance Spectroscopy in aqueous electrolyte solutions shows that films with aggregated particle domains degrade with time and don’t provide long-term corrosion protection of the substrate. However, films with highly dispersed particles have high barrier properties for corrosive species. The comparison of films containing silica-polystyrene composite particles with and without 8-hydroxyquinoline shows higher electrochemical impedances when the inhibitor is present in the film. By applying the Scanning Vibrating Electrode Technique the localized corrosion rate in the fractured area of scratched polymer films containing the silica-polymer-inhibitor composite particles is studied. Electrochemical corrosion cannot be suppressed but the rate is lowered when inhibitor filled composite particles are present in the film. By depositing six polyelectrolyte layers on particle stabilized emulsion droplets their surface morphology changes significantly as shown by SEM visualization. When the oil wettability of the outer polyelectrolyte layer increases, the polyelectrolyte coated droplets can act as emulsion stabilizers themselves by attaching onto bigger oil droplets in a closely packed arrangement. In the presence of 3 mM LaCl3 8-HQ hydrophobized silica particles aggregate strongly on the oil-water inter-face. The application of an ultrasonic field can remove two dimensional shell-compartments from the droplet surface, which are then found in the aqueous bulk phase. Their size ranges up to 1/4th of the spherical particle shell.
Business process models are used within a range of organizational initiatives, where every stakeholder has a unique perspective on a process and demands the respective model. As a consequence, multiple process models capturing the very same business process coexist. Keeping such models in sync is a challenge within an ever changing business environment: once a process is changed, all its models have to be updated. Due to a large number of models and their complex relations, model maintenance becomes error-prone and expensive. Against this background, business process model abstraction emerged as an operation reducing the number of stored process models and facilitating model management. Business process model abstraction is an operation preserving essential process properties and leaving out insignificant details in order to retain information relevant for a particular purpose. Process model abstraction has been addressed by several researchers. The focus of their studies has been on particular use cases and model transformations supporting these use cases. This thesis systematically approaches the problem of business process model abstraction shaping the outcome into a framework. We investigate the current industry demand in abstraction summarizing it in a catalog of business process model abstraction use cases. The thesis focuses on one prominent use case where the user demands a model with coarse-grained activities and overall process ordering constraints. We develop model transformations that support this use case starting with the transformations based on process model structure analysis. Further, abstraction methods considering the semantics of process model elements are investigated. First, we suggest how semantically related activities can be discovered in process models-a barely researched challenge. The thesis validates the designed abstraction methods against sets of industrial process models and discusses the method implementation aspects. Second, we develop a novel model transformation, which combined with the related activity discovery allows flexible non-hierarchical abstraction. In this way this thesis advocates novel model transformations that facilitate business process model management and provides the foundations for innovative tool support.
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.
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.