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Sterisch anspruchsvolle Cyclopentadienyl-Liganden wurden zur Stabilisierung neuer Mono(cyclopentadienyl) Verbindungen der schweren Erdalkalimetalle eingesetzt und deren Funktionalisierbarkeit dieser Spezies wurde exemplarisch durch die Synthese neutraler Tripeldecker-Sandwichkomplexe demonstriert. Die dabei ausgebildeten Molekülstrukturen lassen sich mittels DFT-Rechnungen zuverlässig vorhersagen. In diesem Zusammenhang wurde ebenfalls der Cyclononatetraenyl-Ligand, dessen Komplexeigenschaften bisher nur unzureichend untersucht wurden, eingesetzt. Im Rahmen dieser Arbeit gelang die Synthese des Bis(cyclononatetraenyl)bariums, Ba(C9H9)2, und dessen spektroskopische Charakterisierung. DFT-Rechnungen sagen für diesen Komplex eine Metallocenstruktur mit nahezu parallelen Ringen und einem Ba-Ring Abstand von 2.37 Å voraus. Durch den Einsatz des Tetraisopropylcyclopentadienyl (4Cp) und Tri(tert.-butyl)cyclopentadienyl (Cp’)-Liganden gelang die Synthese von Bis- und Monocyclopentadienyl-Verbindungen der frühen und späten Lanthanoide. Besonders interessant in diesem Zusammenhang ist die erfolgreiche Darstellung des Azido-Clusters, [Na(dme)3]2[4Cp6Yb6(N3)14] (4Cp= (Me2CH)4C5H), der die unterschiedlichen Koordinationsmöglichkeiten des Azido-Liganden in einem einzigen Komplex vereint. Vergleichbare Komplexe waren in der Organolanthanoidchemie bisher unbekannt. Durch Substitution am Cyclopentadienyl-System lassen sich dessen elektronische und sterische Eigenschaften signifikant verändern. Die Auswirkungen dieser Effekte können sehr eindrucksvoll an Manganocen-Komplexen demonstriert werden, in denen sich der low- und high-spin Zustand energetisch nur sehr wenig unterscheiden. Der elektronische Grundzustand einer Reihe unterschiedlich substituierter Manganocen-Komplexe wurde mittels Festkörpermagnetismus, ESR, Röntgenstrukturanalyse, EXAFS und variabler Temperatur UV-Vis Spektroskopie bestimmt, und mit dem Substitutionsmuster am Cyclopentadienyl-System korreliert. Spin-Gleichgewichte ließen sich für [(Me3C)C5H4]2Mn, [(Me3C)2C5H3]2Mn und [(Me3C)(Me3Si)C5H3]2Mn nachweisen. Theoretische Rechnungen postulieren, dass Cerocen, Ce(C8H8)2, ein Beispiel für Moleküle mit gemischt-konfiguriertem Grundzustand sei, der durch 80 % [(Ce)f1e2u(cot)e2u3] und 20 % [(Ce)f0e2u(cot)e2u4] beschreiben werden könne. Obwohl dieses Molekül bereits seit 1976 bekannt ist, ist dessen elektronische Struktur bis heute sehr umstritten. Im Rahmen dieser Arbeit wurden neue Synthesekonzepte für diese Verbindung entwickelt und die elektronische Struktur mittels magnetischer Messungen im Festkörper, EXAFS und XANES Studien untersucht. Die dabei erhaltenen Daten sind in sehr guter Übereinstimmung mit den theoretischen Rechnungen und belegen die Bedeutung eines gemischt-konfigurierten Grundzustandes bei der Bindung in Organometallkomplexen der f-Block Metalle. Während in Cerocen nur ein temperaturunabhängiger Paramagnetismus (TIP) beobachtet werden kann, findet man eine starke Temperaturabhängigkeit der magnetischen Suszeptibilität in Ytterbium Systemen des Typs Cp’2Yb(bipy’) [Cp´ und bipy´ sind substituierte Cyclopentadienyl- oder 4,4’-substituierter 2,2’-Bipyridyl-Liganden]. Temperaturabhängige XANES-Experimenten belegen, dass auch in diesen Systemen ein gemischt-konfigurierter Grundzustand vorliegt, der durch [(Yb)f14(bipy)b1()0] und [(Yb)f13(bipy)b1()1] beschreiben werden kann. Der relative Anteil beider Wellenfunktionen zum Grundzustand wird durch Substitution am 2,2’-Bipyridyl- oder Cyclopentadienyl-System signifikant beeinflusst. Modelle, mit denen sich dieses Verhalten qualitativ beschreiben lässt, wurden im Rahmen dieser Arbeit entwickelt. Ein kinetisch stabilisiertes, adduktfreies Titanocen wurde unter Verwendung des Di(tert.-butyl)cyclopentadienyl Liganden hergestellt und dessen Reaktivität gegenüber kleinen Molekülen, z.B. CO, N2 und H2 untersucht. Im Rahmen der Reaktivitätsstudien wurden ebenfalls 2,2’-Bipyridyl Addukte an das Cp’2Ti Fragment synthetisiert und deren magnetische Eigenschaften erforscht. Durch Variationen am 2,2’-Bipyridyl System lässt sich das Singlet-Triplet Splitting in diesem System gezielt steuern.

Fragmentation of tropical rain forests is pervasive and results in various modifications in the ecosystem functioning such as … It has long been noticed that the colony densities of a dominant herbivore in the neotropics - leaf-cutting ant (LCA) - increase in fragmentation-related habitats like forest edges and small fragments, however the reasons for this increase are not clear. The aim of the study was to test the hypothesis that bottom-up control of LCA populations is less effective in fragmented compared to continuous forests and thus explains the increase in LCA colony densities in these habitats. In order to test for less effective bottom-up control, I proposed four working hypotheses. I hypothesized that LCA colonies in fragmented habitats (1) find more palatable vegetation due to low plant defences, (2) forage on few dominant species resulting in a narrow diet breadth, (3) possess small foraging areas and (4) increase herbivory rate at the colony level. The study was conducted in the remnants of the Atlantic rainforest in NE Brazil. Two fragmentation-related forest habitats were included: the edge and a 3500-ha continuous forest and the interior of the 50-ha forest fragment. The interior of the continuous forest served as a control habitat for the study. All working hypotheses can be generally accepted. The results indicate that the abundance of LCA host plant species in the habitats created by forest fragmentation along with weaker chemical defense of those species (especially the lack of terpenoids) allow ants to forage predominantly on palatable species and thus reduce foraging costs on other species. This is supported by narrower ant diet breadth in these habitats. Similarly, small foraging areas in edge habitats and in small forest fragments indicate that there ants do not have to go far to find the suitable host species and thus they save foraging costs. Increased LCA herbivory rates indicate that the damages (i.e., amount of harvested foliage) caused by LCA are more important in fragmentation-related habitats which are more vulnerable to LCA herbivory due to the high availability of palatable plants and a low total amount of foliage (LAI). (1) Few plant defences, (2) narrower ant diet breadth, (3) reduced colony foraging areas, and (4) increased herbivory rates, clearly indicate a weaker bottom-up control for LCA in fragmented habitats. Weak bottom-up control in the fragmentation-related habitats decreases the foraging costs of a LCA colony in these habitats and the colonies might use the surplus of energy resulting from reduced foraging costs to increase the colony growth, the reproduction and turnover. If correct, this explains why fragmented habitats support more LCA colonies at a given time compared to continuous forest habitats. Further studies are urgently needed to estimate LCA colony growth and turnover rates. There are indices that edge effects of forest fragmentation might be more responsible in regulating LCA populations than area or isolation effects. This emphasizes the need to conserve big forest fragments not to fall below a critical size and retain their regular shape. Weak bottom-up control of LCA populations has various consequences on forested ecosystems. I suggest a loop between forest fragmentation and LCA population dynamics: the increased LCA colony densities, along with lower bottom-up control increase LCA herbivory pressure on the forest and thus inevitably amplify the deleterious effects of fragmentation. These effects include direct consequences of leaf removal by ants and various indirect effects on ecosystem functioning. This study contributes to our understanding of how primary fragmentation effects, via the alteration of trophic interactions, may translate into higher order effects on ecosystem functions.

Competing Neural Networks as Models for Non Stationary Financial Time Series -Changepoint Analysis-
(2005)

The problem of structural changes (variations) play a central role in many scientific fields. One of the most current debates is about climatic changes. Further, politicians, environmentalists, scientists, etc. are involved in this debate and almost everyone is concerned with the consequences of climatic changes. However, in this thesis we will not move into the latter direction, i.e. the study of climatic changes. Instead, we consider models for analyzing changes in the dynamics of observed time series assuming these changes are driven by a non-observable stochastic process. To this end, we consider a first order stationary Markov Chain as hidden process and define the Generalized Mixture of AR-ARCH model(GMAR-ARCH) which is an extension of the classical ARCH model to suit to model with dynamical changes. For this model we provide sufficient conditions that ensure its geometric ergodic property. Further, we define a conditional likelihood given the hidden process and a pseudo conditional likelihood in turn. For the pseudo conditional likelihood we assume that at each time instant the autoregressive and volatility functions can be suitably approximated by given Feedfoward Networks. Under this setting the consistency of the parameter estimates is derived and versions of the well-known Expectation Maximization algorithm and Viterbi Algorithm are designed to solve the problem numerically. Moreover, considering the volatility functions to be constants, we establish the consistency of the autoregressive functions estimates given some parametric classes of functions in general and some classes of single layer Feedfoward Networks in particular. Beside this hidden Markov Driven model, we define as alternative a Weighted Least Squares for estimating the time of change and the autoregressive functions. For the latter formulation, we consider a mixture of independent nonlinear autoregressive processes and assume once more that the autoregressive functions can be approximated by given single layer Feedfoward Networks. We derive the consistency and asymptotic normality of the parameter estimates. Further, we prove the convergence of Backpropagation for this setting under some regularity assumptions. Last but not least, we consider a Mixture of Nonlinear autoregressive processes with only one abrupt unknown changepoint and design a statistical test that can validate such changes.

In many industrial applications fast and accurate solutions of linear elliptic partial differential equations are needed as one of the building blocks of more complex problems. The domains are often highly complex and meshing turns out to be expensive and difficult to obtain with a sufficient quality. In such cases methods with a regular, not boundary adapted grid offer an attractive alternative. The Explicit Jump Immersed Interface Method is one of these algorithms. The main interest of this work lies in solving the linear elasticity equations. For this purpose the existing EJIIM algorithm has been extended to three dimensions. The Poisson equation is always considered in parallel as the most typical representative of elliptic PDEs. During the work it became clear that EJIIM can have very high computational memory requirements. To overcome this problem an improvement, Reduced EJIIM is proposed. The main theoretical result in this work is the proof of the smoothing property of inverses of elliptic finite difference operators in two and three space dimensions. It is an often observed phenomena that the local truncation error is allowed to be of lower order along some lower dimensional manifold without influencing the global convergence order of the solution.

Under physiological conditions oxygen is constantly being converted to reactive oxygen intermediates, in mitochondria, peroxisomes, cytochrome p450 systems, macrophages, neutrophils and in plasma membranes. These reactive oxygen species (ROS) are toxic and therefore alter cell integrity leading to cell damage. To protect itself against this toxic effect of ROS, living systems have developed defence systems that scavenge ROS formation. These systems include some enzymes, transporting proteins and small antioxidant molecules for instance vitamin C and E. This thesis describes a study on the antioxidant chemistry and activity of vitamin C in vivo and in vitro systems using ESR spectroscopy. Also, a new method was designed to label ascorbic acid with a fluorescent marker. Moreover, some important criteria were considered for the evaluation and quantification of ascorbyl radicals in human blood plasma using two types of ESR spectrometers.

The aim of the thesis is the numerical investigation of saturated, stationary, incompressible Newtonian flow in porous media when inertia is not negligible. We focus our attention to the Navier-Stokes system with two pressures derived by two-scale homogenization. The thesis is subdivided into five Chapters. After the introductory remarks on porous media, filtration laws and upscaling methods, the first chapter is closed by stating the basic terminology and mathematical fundamentals. In Chapter 2, we start by formulating the Navier-Stokes equations on a periodic porous medium. By two-scale expansions of the velocity and pressure, we formally derive the Navier-Stokes system with two pressures. For the sake of completeness, known existence and uniqueness results are repeated and a convergence proof is given. Finally, we consider Stokes and Navier-Stokes systems with two pressures with respect to their relation to Darcy's law. Chapter 3 and Chapter 4 are devoted to the numerical solution of the nonlinear two pressure system. Therefore, we follow two approaches. The first approach which is developed in Chapter 3 is based on a splitting of the Navier-Stokes system with two pressures into micro and macro problems. The splitting is achieved by Taylor expanding the permeability function or by discretely computing the permeability function. The problems to be solved are a series of Stokes and Navier-Stokes problems on the periodicity cell. The Stokes problems are solved by an Uzawa conjugate gradient method. The Navier-Stokes equations are linearized by a least-squares conjugate gradient method, which leads to the solution of a sequence of Stokes problems. The macro problem consists of solving a nonlinear uniformly elliptic equation of second order. The least-squares linearization is applied to the macro problem leading to a sequence of Poisson problems. All equations will be discretized by finite elements. Numerical results are presented at the end of Chapter 3. The second approach presented in Chapter 4 relies on the variational formulation in a certain Hilbert space setting of the Navier-Stokes system with two pressures. The nonlinear problem is again linearized by the least-squares conjugate gradient method. We obtain a sequence of Stokes systems with two pressures. For the latter systems, we propose a fast solution method which relies on pre-computing Stokes systems on the periodicity cell for finite element basis functions acting as right hand sides. Finally, numerical results are discussed. In Chapter 5 we are concerned with modeling and simulation of the pressing section of a paper machine. We state a two-dimensional model of a press nip which takes into account elasticity and flow phenomena. Nonlinear filtration laws are incorporated into the flow model. We present a numerical solution algorithm and the chapter is closed by a numerical investigation of the model with special focus on inertia effects.

In conventional radio communication systems, the system design generally starts from the transmitter (Tx), i.e. the signal processing algorithm in the transmitter is a priori selected, and then the signal processing algorithm in the receiver is a posteriori determined to obtain the corresponding data estimate. Therefore, in these conventional communication systems, the transmitter can be considered the master and the receiver can be considered the slave. Consequently, such systems can be termed transmitter (Tx) oriented. In the case of Tx orientation, the a priori selected transmitter algorithm can be chosen with a view to arrive at particularly simple transmitter implementations. This advantage has to be countervailed by a higher implementation complexity of the a posteriori determined receiver algorithm. Opposed to the conventional scheme of Tx orientation, the design of communication systems can alternatively start from the receiver (Rx). Then, the signal processing algorithm in the receiver is a priori determined, and the transmitter algorithm results a posteriori. Such an unconventional approach to system design can be termed receiver (Rx) oriented. In the case of Rx orientation, the receiver algorithm can be a priori selected in such a way that the receiver complexity is minimum, and the a posteriori determined transmitter has to tolerate more implementation complexity. In practical communication systems the implementation complexity corresponds to the weight, volume, cost etc of the equipment. Therefore, the complexity is an important aspect which should be taken into account, when building practical communication systems. In mobile radio communication systems, the complexity of the mobile terminals (MTs) should be as low as possible, whereas more complicated implementations can be tolerated in the base station (BS). Having in mind the above mentioned complexity features of the rationales Tx orientation and Rx orientation, this means that in the uplink (UL), i.e. in the radio link from the MT to the BS, the quasi natural choice would be Tx orientation, which leads to low cost transmitters at the MTs, whereas in the downlink (DL), i.e. in the radio link from the BS to the MTs, the rationale Rx orientation would be the favorite alternative, because this results in simple receivers at the MTs. Mobile radio downlinks with the rationale Rx orientation are considered in the thesis. Modern mobile radio communication systems are cellular systems, in which both the intracell and intercell interferences exist. These interferences are the limiting factors for the performance of mobile radio systems. The intracell interference can be eliminated or at least reduced by joint signal processing with consideration of all the signals in the considered cell. However such joint signal processing is not feasible for the elimination of intercell interference in practical systems. Knowing that the detrimental effect of intercell interference grows with its average energy, the transmit energy radiated from the transmitter should be as low as possible to keep the intercell interference low. Low transmit energy is required also with respect to the growing electro-phobia of the public. The transmit energy reduction for multi-user mobile radio downlinks by the rationale Rx orientation is dealt with in the thesis. Among the questions still open in this research area, two questions of major importance are considered here. MIMO is an important feature with respect to the transmit power reduction of mobile radio systems. Therefore, first questionconcerns the linear Rx oriented transmission schemes combined with MIMO antenna structures. The investigations of the MIMO benefit on the linear Rx oriented transmission schemes are studied in the thesis. Utilization of unconventional multiply connected quantization schemes at the receiver has also great potential to reduce the transmit energy. Therefore, the second question considers the designing of non-linear Rx oriented transmission schemes combined with multiply connected quantization schemes.

Since its invention by Sir Allistair Pilkington in 1952, the float glass process has been used to manufacture long thin flat sheets of glass. Today, float glass is very popular due to its high quality and relatively low production costs. When producing thinner glass the main concern is to retain its optical quality, which can be deteriorated during the manufacturing process. The most important stage of this process is the floating part, hence is considered to be responsible for the loss in the optical quality. A series of investigations performed on the finite products showed the existence of many short wave patterns, which strongly affect the optical quality of the glass. Our work is concerned with finding the mechanism for wave development, taking into account all possible factors. In this thesis, we model the floating part of the process by an theoretical study of the stability of two superposed fluids confined between two infinite plates and subjected to a large horizontal temperature gradient. Our approach is to take into account the mixed convection effects (viscous shear and buoyancy), neglecting on the other hand the thermo-capillarity effects due to the length of our domain and the presence of a small stabilizing vertical temperature gradient. Both fluids are treated as Newtonian with constant viscosity. They are immiscible, incompressible, have very different properties and have a free surface between them. The lower fluid is a liquid metal with a very small kinematic viscosity, whereas the upper fluid is less dense. The two fluids move with different velocities: the speed of the upper fluid is imposed, whereas the lower fluid moves as a result of buoyancy effects. We examine the problem by means of small perturbation analysis, and obtain a system of two Orr-Sommerfeld equations coupled with two energy equations, and general interface and boundary conditions. We solve the system analytically in the long- and short- wave limit, by using asymptotic expansions with respect to the wave number. Moreover, we write the system in the form of a general eigenvalue problem and we solve the system numerically by using Chebyshev spectral methods for fluid dynamics. The results (both analytical and numerical) show the existence of the small-amplitude travelling waves, which move with constant velocity for wave numbers in the intermediate range. We show that the stability of the system is ensured in the long wave limit, a fact which is in agreement with the real float glass process. We analyze the stability for a wide range of wave numbers, Reynolds, Weber and Grashof number, and explain the physical implications on the dynamics of the problem. The consequences of the linear stability results are discussed. In reality in the float glass process, the temperature strongly influences the viscosity of both molten metal and hot glass, which will have direct consequences on the stability of the system. We investigate the linear stability of two superposed fluids with temperature dependent viscosities by considering a different model for the viscosity dependence of each fluid. Although, the temperature-viscosity relationships for glass and metal are more complex than those used in our computations, our intention is to emphasize the effects of this dependence on the stability of the system. It is known from the literature that in the case of one fluid, the heat, which causes viscosity to decrease along the domain, usually destabilizes the flow. For the two superposed fluids problem we investigate this behaviour and discuss the consequences of the linear stability in this new case.

Over the last decades, mathematical modeling has reached nearly all fields of natural science. The abstraction and reduction to a mathematical model has proven to be a powerful tool to gain a deeper insight into physical and technical processes. The increasing computing power has made numerical simulations available for many industrial applications. In recent years, mathematicians and engineers have turned there attention to model solid materials. New challenges have been found in the simulation of solids and fluid-structure interactions. In this context, it is indispensable to study the dynamics of elastic solids. Elasticity is a main feature of solid bodies while demanding a great deal of the numerical treatment. There exists a multitude of commercial tools to simulate the behavior of elastic solids. Anyhow, the majority of these software packages consider quasi-stationary problems. In the present work, we are interested in highly dynamical problems, e.g. the rotation of a solid. The applicability to free-boundary problems is a further emphasis of our considerations. In the last years, meshless or particle methods have attracted more and more attention. In many fields of numerical simulation these methods are on a par with classical methods or superior to them. In this work, we present the Finite Pointset Method (FPM) which uses a moving least squares particle approximation operator. The application of this method to various industrial problems at the Fraunhofer ITWM has shown that FPM is particularly suitable for highly dynamical problems with free surfaces and strongly changing geometries. Thereby, FPM offers exactly the features that we require for the analysis of the dynamics of solid bodies. In the present work, we provide a numerical scheme capable to simulate the behavior of elastic solids. We present the system of partial differential equations describing the dynamics of elastic solids and show its hyperbolic character. In particular, we focus our attention to the constitutive law for the stress tensor and provide evolution equations for the deviatoric part of the stress tensor in order to circumvent limitations of the classical Hooke's law. Furthermore, we present the basic principle of the Finite Pointset Method. In particular, we provide the concept of upwinding in a given direction as a key ingredient for stabilizing hyperbolic systems. The main part of this work describes the design of a numerical scheme based on FPM and an operator splitting to take the different processes within a solid body into account. Each resulting subsystem is treated separately in an adequate way. Hereby, we introduce the notion of system-inherent directions and dimensional upwinding. Finally, a coupling strategy for the subsystems and results are presented. We close this work with some final conclusions and an outlook on future work.

The HMG-CoA reductase inhibitors SIM, LOV, ATV, PRA, FV and NKS were investigated for their effects on human SkMCs. We were able to demonstrate that statins can induce oxidative stress (ROS formation, GSH-depletion, TBARS), apoptosis (, caspase-3 activity, nuclear morphology) and necrosis (LDH-leakage) in hSkMCs. After incubation with statins, the sequence of cellular events starts by the increased formation of ROS (30 min) followed by caspase-3 activation (2-4 hours) and necrosis (LDH-leakage) and formation of condensed and fragmented nuclei after 24-72 hours. It was shown that, antioxidants (NAC, DTT, TPGS, M-2 and M-3) and the HMG-CoA reductase downstream metabolites (MVA, F, FPP, GG and GGPP) protected against statin-induced ROS formation, caspase-3 activation and partially from necrosis. The caspase-3 inhibitor Ac-DEVD-CHO rescues cells partially from necrosis. These results suggest that the statin-induced necrosis is HMG-CoA dependent and occurs secondary to apoptosis, which by decrease of ATP is driven into necrosis. The increase of ATP observed at low concentrations and early time points suggest an increased glycolytic activity. This was confirmed by increased PDK-4 gene expression and increased PFK2/F-2,6-BPase expression both activator of glycolysis. Glycolysis was also confirmed for some statins by increased cellular lactate concentations. The consequence of PDK-4 mediated pyruvate dehydrogenase inactivation is the metabolic switching from fatty acid to amino acid from proteins as energy source. The oxidative stress hypothesis was further supported by the induction of the FOXO3A transcription factor, which is involved in regulating MnSOD-2 expression in the mitochondrium. The mechanism by which statins produce ROS is still not resolved. There is an indirect evidence from our experiments as well as from the literature, that immediately after the statin treatment, intracellular Ca2+ is mobilized due to HMG-CoA reductase inhibition, which after mitochondrial uptake could lead to increased ROS formation.