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This work presents mathematical and computational approaches to cover various aspects of metabolic network modelling, especially regarding the limited availability of detailed kinetic knowledge on reaction rates. It is shown that precise mathematical formulations of problems are needed i) to find appropriate and, if possible, efficient algorithms to solve them, and ii) to determine the quality of the found approximate solutions. Furthermore, some means are introduced to gain insights on dynamic properties of metabolic networks either directly from the network structure or by additionally incorporating steady-state information. Finally, an approach to identify key reactions in a metabolic networks is introduced, which helps to develop simple yet useful kinetic models. The rise of novel techniques renders genome sequencing increasingly fast and cheap. In the near future, this will allow to analyze biological networks not only for species but also for individuals. Hence, automatic reconstruction of metabolic networks provides itself as a means for evaluating this huge amount of experimental data. A mathematical formulation as an optimization problem is presented, taking into account existing knowledge and experimental data as well as the probabilistic predictions of various bioinformatical methods. The reconstructed networks are optimized for having large connected components of high accuracy, hence avoiding fragmentation into small isolated subnetworks. The usefulness of this formalism is exemplified on the reconstruction of the sucrose biosynthesis pathway in Chlamydomonas reinhardtii. The problem is shown to be computationally demanding and therefore necessitates efficient approximation algorithms. The problem of minimal nutrient requirements for genome-scale metabolic networks is analyzed. Given a metabolic network and a set of target metabolites, the inverse scope problem has as it objective determining a minimal set of metabolites that have to be provided in order to produce the target metabolites. These target metabolites might stem from experimental measurements and therefore are known to be produced by the metabolic network under study, or are given as the desired end-products of a biotechological application. The inverse scope problem is shown to be computationally hard to solve. However, I assume that the complexity strongly depends on the number of directed cycles within the metabolic network. This might guide the development of efficient approximation algorithms. Assuming mass-action kinetics, chemical reaction network theory (CRNT) allows for eliciting conclusions about multistability directly from the structure of metabolic networks. Although CRNT is based on mass-action kinetics originally, it is shown how to incorporate further reaction schemes by emulating molecular enzyme mechanisms. CRNT is used to compare several models of the Calvin cycle, which differ in size and level of abstraction. Definite results are obtained for small models, but the available set of theorems and algorithms provided by CRNT can not be applied to larger models due to the computational limitations of the currently available implementations of the provided algorithms. Given the stoichiometry of a metabolic network together with steady-state fluxes and concentrations, structural kinetic modelling allows to analyze the dynamic behavior of the metabolic network, even if the explicit rate equations are not known. In particular, this sampling approach is used to study the stabilizing effects of allosteric regulation in a model of human erythrocytes. Furthermore, the reactions of that model can be ranked according to their impact on stability of the steady state. The most important reactions in that respect are identified as hexokinase, phosphofructokinase and pyruvate kinase, which are known to be highly regulated and almost irreversible. Kinetic modelling approaches using standard rate equations are compared and evaluated against reference models for erythrocytes and hepatocytes. The results from this simplified kinetic models can simulate acceptably the temporal behavior for small changes around a given steady state, but fail to capture important characteristics for larger changes. The aforementioned approach to rank reactions according to their influence on stability is used to identify a small number of key reactions. These reactions are modelled in detail, including knowledge about allosteric regulation, while all other reactions were still described by simplified reaction rates. These so-called hybrid models can capture the characteristics of the reference models significantly better than the simplified models alone. The resulting hybrid models might serve as a good starting point for kinetic modelling of genome-scale metabolic networks, as they provide reasonable results in the absence of experimental data, regarding, for instance, allosteric regulations, for a vast majority of enzymatic reactions.
A huge number of applications require coherent radiation in the visible spectral range. Since diode lasers are very compact and efficient light sources, there exists a great interest to cover these applications with diode laser emission. Despite modern band gap engineering not all wavelengths can be accessed with diode laser radiation. Especially in the visible spectral range between 480 nm and 630 nm no emission from diode lasers is available, yet. Nonlinear frequency conversion of near-infrared radiation is a common way to generate coherent emission in the visible spectral range. However, radiation with extraordinary spatial temporal and spectral quality is required to pump frequency conversion. Broad area (BA) diode lasers are reliable high power light sources in the near-infrared spectral range. They belong to the most efficient coherent light sources with electro-optical efficiencies of more than 70%. Standard BA lasers are not suitable as pump lasers for frequency conversion because of their poor beam quality and spectral properties. For this purpose, tapered lasers and diode lasers with Bragg gratings are utilized. However, these new diode laser structures demand for additional manufacturing and assembling steps that makes their processing challenging and expensive. An alternative to BA diode lasers is the stripe-array architecture. The emitting area of a stripe-array diode laser is comparable to a BA device and the manufacturing of these arrays requires only one additional process step. Such a stripe-array consists of several narrow striped emitters realized with close proximity. Due to the overlap of the fields of neighboring emitters or the presence of leaky waves, a strong coupling between the emitters exists. As a consequence, the emission of such an array is characterized by a so called supermode. However, for the free running stripe-array mode competition between several supermodes occurs because of the lack of wavelength stabilization. This leads to power fluctuations, spectral instabilities and poor beam quality. Thus, it was necessary to study the emission properties of those stripe-arrays to find new concepts to realize an external synchronization of the emitters. The aim was to achieve stable longitudinal and transversal single mode operation with high output powers giving a brightness sufficient for efficient nonlinear frequency conversion. For this purpose a comprehensive analysis of the stripe-array devices was done here. The physical effects that are the origin of the emission characteristics were investigated theoretically and experimentally. In this context numerical models could be verified and extended. A good agreement between simulation and experiment was observed. One way to stabilize a specific supermode of an array is to operate it in an external cavity. Based on mathematical simulations and experimental work, it was possible to design novel external cavities to select a specific supermode and stabilize all emitters of the array at the same wavelength. This resulted in stable emission with 1 W output power, a narrow bandwidth in the range of 2 MHz and a very good beam quality with M²<1.5. This is a new level of brightness and brilliance compared to other BA and stripe-array diode laser systems. The emission from this external cavity diode laser (ECDL) satisfied the requirements for nonlinear frequency conversion. Furthermore, a huge improvement to existing concepts was made. In the next step newly available periodically poled crystals were used for second harmonic generation (SHG) in single pass setups. With the stripe-array ECDL as pump source, more than 140 mW of coherent radiation at 488 nm could be generated with a very high opto-optical conversion efficiency. The generated blue light had very good transversal and longitudinal properties and could be used to generate biphotons by parametric down-conversion. This was feasible because of the improvement made with the infrared stripe-array diode lasers due to the development of new physical concepts.
Water shortage is a serious threat for many societies worldwide. In drylands, water management measures like the construction of reservoirs are affected by eroded sediments transported in the rivers. Thus, the capability of assessing water and sediment fluxes at the river basin scale is of vital importance to support management decisions and policy making. This subject was addressed by the DFG-funded SESAM-project (Sediment Export from large Semi-Arid catchments: Measurements and Modelling). As a part of this project, this thesis focuses on (1) the development and implementation of an erosion module for a meso-scale catchment model, (2) the development of upscaling and generalization methods for the parameterization of such model, (3) the execution of measurements to obtain data required for the modelling and (4) the application of the model to different study areas and its evaluation. The research was carried out in two meso-scale dryland catchments in NE-Spain: Ribera Salada (200 km²) and Isábena (450 km²). Adressing objective 1, WASA-SED, a spatially semi-distributed model for water and sediment transport at the meso-scale was developed. The model simulates runoff and erosion processes at the hillslope scale, transport processes of suspended and bedload fluxes in the river reaches, and retention and remobilisation processes of sediments in reservoirs. This thesis introduces the model concept, presents current model applications and discusses its capabilities and limitations. Modelling at larger scales faces the dilemma of describing relevant processes while maintaining a manageable demand for input data and computation time. WASA-SED addresses this challenge by employing an innovative catena-based upscaling approach: the landscape is represented by characteristic toposequences. For deriving these toposequences with regard to multiple attributes (eg. topography, soils, vegetation) the LUMP-algorithm (Landscape Unit Mapping Program) was developed and related to objective 2. It incorporates an algorithm to retrieve representative catenas and their attributes, based on a Digital Elevation Model and supplemental spatial data. These catenas are classified to provide the discretization for the WASA-SED model. For objective 3, water and sediment fluxes were monitored at the catchment outlet of the Isábena and some of its sub-catchments. For sediment yield estimation, the intermittent measurements of suspended sediment concentration (SSC) had to be interpolated. This thesis presents a comparison of traditional sediment rating curves (SRCs), generalized linear models (GLMs) and non-parametric regression using Random Forests (RF) and Quantile Regression Forests (QRF). The observed SSCs are highly variable and range over six orders of magnitude. For these data, traditional SRCs performed poorly, as did GLMs, despite including other relevant process variables (e.g. rainfall intensities, discharge characteristics). RF and QRF proved to be very robust and performed favourably for reproducing sediment dynamics. QRF additionally excels in providing estimates on the accuracy of the predictions. Subsequent analysis showed that most of the sediment was exported during intense storms of late summer. Later floods yielded successively less sediment. Comparing sediment generation to yield at the outlet suggested considerable storage effects within the river channel. Addressing objective 4, the WASA-SED model was parameterized for the two study areas in NE Spain and applied with different foci. For Ribera Salada, the uncalibrated model yielded reasonable results for runoff and sediment. It provided quantitative measures of the change in runoff and sediment yield for different land-uses. Additional land management scenarios were presented and compared to impacts caused by climate change projections. In contrast, the application for the Isábena focussed on exploring the full potential of the model's predictive capabilities. The calibrated model achieved an acceptable performance for the validation period in terms of water and sediment fluxes. The inadequate representation of the lower sub-catchments inflicted considerable reductions on model performance, while results for the headwater catchments showed good agreement despite stark contrasts in sediment yield. In summary, the application of WASA-SED to three catchments proved the model framework to be a practicable multi-scale approach. It successfully links the hillslope to the catchment scale and integrates the three components hillslope, river and reservoir in one model. Thus, it provides a feasible approach for tackling issues of water and sediment yield at the meso-scale. The crucial role of processes like transmission losses and sediment storage in the river has been identified. Further advances can be expected when the representation of connectivity of water and sediment fluxes (intra-hillslope, hillslope-river, intra-river) is refined and input data improves.