### Filtern

#### Erscheinungsjahr

- 2002 (16) (entfernen)

#### Dokumenttyp

- Dissertation (16) (entfernen)

#### Sprache

- Englisch (16) (entfernen)

#### Schlagworte

- Adaptive Antennen (1)
- Anti-diffusion (1)
- Antidiffusion (1)
- Chromatin (1)
- Chromatographiesäule (1)
- Consistencyanalysis (1)
- DNA adducts (1)
- Diffusion (1)
- Dissertation (1)
- Efficiency (1)

#### Fachbereich / Organisatorische Einheit

thesis deals with the investigation of the dynamics of optically excited (hot) electrons in thin and ultra-thin layers. The main interests concern about the time behaviour of the dissipation of energy and momentum of the excited electrons. The relevant relaxation times occur in the femtosecond time region. The two-photon photoemission is known to be an adequate tool in order to analyse such dynamical processes in real-time. This work expands the knowledge in the fields of electron relaxation in ultra-thin silver layers on different substrates, as well as in adsorbate states in a bandgap of a semiconductor. It contributes facts to the comprehension of spin transport through an interface between a metal and a semiconductor. The primary goal was to prove the predicted theory by reducing the observed crystal in at least one direction. One expects a change of the electron relaxation behaviour while altering the crystal’s shape from a 3d bulk to a 2d (ultra-thin) layer. This is due to the fact that below a determined layer thickness, the electron gas transfers to a two-dimensional one. This behaviour could be proven in this work. In an about 3nm thin silver layer on graphite, the hot electrons show a jump to longer relaxation time all over the whole accessible energy range. It is the first time that the temporal evolution of the relaxation of excited electrons could be observed during the transition from a 3d to a 2d system. In order to reduce or even eliminate the influence coming from the substrate, the system of silver on the semiconductor GaAs, which has a bandgap of 1.5eV at the Gamma-point, was investigated. The observations of the relaxation behaviour of hot electron in different ultra-thin silver layers on this semiconductor could show, that at metal-insulator-junctions, plasmons in the silver and in the interface, as well as cascading electrons from higher lying energies, have a huge influence to the dissipation of momentum and energy. This comes mainly from the band bending of the semiconductor, and from the electrons, which are excited in GaAs. The limitation of the silver layer on GaAs in one direction led to the expected generation of quantum well states (QWS) in the bandgap. Those adsorbate states have quantised energy- and momentum values, which are directly connected to the layer thickness and the standing electron wave therein. With the experiments of this work, published values could not only be completed and proved, but it could also be determined the time evolution of such a QWS. It came out that this QWS might only be filled by electrons, which are moving from the lower edge of the conduction band of the semiconductor to the silver and suffer cascading steps there. By means of the system silver on GaAs, and of the known fact that an excitation of electrons in GaAs with circularly polarised light of the energy 1.5eV does produce spin polarised electrons in the conduction band, it became possible to bring a contribution to the hot topic of spin injection. The main target of spin injection is the transfer of spin polarised electrons out of a ferromagnet into a semiconductor, in order to develop spin dependent switches and memories. It could be demonstrated here that spin polarised electrons from GaAs can move through the interface into silver, could be photoemitted from there and their spin was still being detectable. As a third investigation system, ultra-thin silver layers were deposited on the insulator MgO, which has a bandgap of 7.8eV. Also in this system, one could recognize a change in the relaxation time while reducing the dimension of the silver layer from thick to ultra-thin. Additionally, it came out an extreme large relaxation time at a layer thickness of 0.6 – 1.2nm. This time is an order of magnitude longer than at thick films, and this is a consequence of two factors: first, the reduction of the phase space due to the confined electron gas in the z-direction, and second, the slowlier thermalisation of the electron gas due to less accessible scattering partners.

The dissertation is concerned with the numerical solution of Fokker-Planck equations in high dimensions arising in the study of dynamics of polymeric liquids. Traditional methods based on tensor product structure are not applicable in high dimensions for the number of nodes required to yield a fixed accuracy increases exponentially with the dimension; a phenomenon often referred to as the curse of dimension. Particle methods or finite point set methods are known to break the curse of dimension. The Monte Carlo method (MCM) applied to such problems are 1/sqrt(N) accurate, where N is the cardinality of the point set considered, independent of the dimension. Deterministic version of the Monte Carlo method called the quasi Monte Carlo method (QMC) are quite effective in integration problems and accuracy of the order of 1/N can be achieved, up to a logarithmic factor. However, such a replacement cannot be carried over to particle simulations due to the correlation among the quasi-random points. The method proposed by Lecot (C.Lecot and F.E.Khettabi, Quasi-Monte Carlo simulation of diffusion, Journal of Complexity, 15 (1999), pp.342-359) is the only known QMC approach, but it not only leads to large particle numbers but also the proven order of convergence is 1/N^(2s) in dimension s. We modify the method presented there, in such a way that the new method works with reasonable particle numbers even in high dimensions and has better order of convergence. Though the provable order of convergence is 1/sqrt(N), the results show less variance and thus the proposed method still slightly outperforms standard MCM.

Matrix Compression Methods for the Numerical Solution of Radiative Transfer in Scattering Media
(2002)

Radiative transfer in scattering media is usually described by the radiative transfer equation, an integro-differential equation which describes the propagation of the radiative intensity along a ray. The high dimensionality of the equation leads to a very large number of unknowns when discretizing the equation. This is the major difficulty in its numerical solution. In case of isotropic scattering and diffuse boundaries, the radiative transfer equation can be reformulated into a system of integral equations of the second kind, where the position is the only independent variable. By employing the so-called momentum equation, we derive an integral equation, which is also valid in case of linear anisotropic scattering. This equation is very similar to the equation for the isotropic case: no additional unknowns are introduced and the integral operators involved have very similar mapping properties. The discretization of an integral operator leads to a full matrix. Therefore, due to the large dimension of the matrix in practical applcation, it is not feasible to assemble and store the entire matrix. The so-called matrix compression methods circumvent the assembly of the matrix. Instead, the matrix-vector multiplications needed by iterative solvers are performed only approximately, thus, reducing, the computational complexity tremendously. The kernels of the integral equation describing the radiative transfer are very similar to the kernels of the integral equations occuring in the boundary element method. Therefore, with only slight modifications, the matrix compression methods, developed for the latter are readily applicable to the former. As apposed to the boundary element method, the integral kernels for radiative transfer in absorbing and scattering media involve an exponential decay term. We examine how this decay influences the efficiency of the matrix compression methods. Further, a comparison with the discrete ordinate method shows that discretizing the integral equation may lead to reductions in CPU time and to an improved accuracy especially in case of small absorption and scattering coefficients or if local sources are present.

Different aspects of geomagnetic field modelling from satellite data are examined in the framework of modern multiscale approximation. The thesis is mostly concerned with wavelet techniques, i.e. multiscale methods based on certain classes of kernel functions which are able to realize a multiscale analysis of the funtion (data) space under consideration. It is thus possible to break up complicated functions like the geomagnetic field, electric current densities or geopotentials into different pieces and study these pieces separately. Based on a general approach to scalar and vectorial multiscale methods, topics include multiscale denoising, crustal field approximation and downward continuation, wavelet-parametrizations of the magnetic field in Mie-representation as well as multiscale-methods for the analysis of time-dependent spherical vector fields. For each subject the necessary theoretical framework is established and numerical applications examine and illustrate the practical aspects.

The immiscible lattice BGK method for solving the two-phase incompressible Navier-Stokes equations is analysed in great detail. Equivalent moment analysis and local differential geometry are applied to examine how interface motion is determined and how surface tension effects can be included such that consistency to the two-phase incompressible Navier-Stokes equations can be expected. The results obtained from theoretical analysis are verified by numerical experiments. Since the intrinsic interface tracking scheme of immiscible lattice BGK is found to produce unsatisfactory results in two-dimensional simulations several approaches to improving it are discussed but all of them turn out to yield no substantial improvement. Furthermore, the intrinsic interface tracking scheme of immiscible lattice BGK is found to be closely connected to the well-known conservative volume tracking method. This result suggests to couple the conservative volume tracking method for determining interface motion with the Navier-Stokes solver of immiscible lattice BGK. Applied to simple flow fields, this coupled method yields much better results than plain immiscible lattice BGK.

One crucial assumption of continuous financial mathematics is that the portfolio can be rebalanced continuously and that there are no transaction costs. In reality, this of course does not work. On the one hand, continuous rebalancing is impossible, on the other hand, each transaction causes costs which have to be subtracted from the wealth. Therefore, we focus on trading strategies which are based on discrete rebalancing - in random or equidistant times - and where transaction costs are considered. These strategies are considered for various utility functions and are compared with the optimal ones of continuous trading.

In this work the investigation of a (Ti, Al, Si) N system was done. The main point of investigation was to study the possibility of getting the nanocomposite coatings structures by deposition of multilayer films from TiN, AlSiN, . This tries to understand the relation between the mechanical properties (hardness, Young s modulus), and the microstructure (nanocrystalline with individual phases). Particularly special attention was given to the temperature effects on microstructural changes in annealing at 600 °C for the coatings. The surface hardness, elastic modulus, and the multilayers diffusion and compositions were the test tools for the comparison between the different coated samples with and without annealing at 600 °C. To achieve this object a rectangular aluminum vacuum chamber with three unbalanced sputtering magnetrons for the deposition of thin film coatings from different materials was constructed The chamber consists mainly of two chambers, the pre-vacuum chamber to load the workpiece, and the main vacuum chamber where the sputtering deposition of the thin film coatings take place. The workpiece is moving on a car travel on a railway between the two chambers to the position of the magnetrons by step motors. The chambers are divided by a self constructed rectangular gate controlled manually from outside the chamber. The chamber was sealed for vacuum use using glue and screws. Therefore, different types of glue were tested not only for its ability to develop an uniform thin layer in the gap between the aluminum plates to seal the chamber for vacuum use, but also low outgassing rates which made it suitable for vacuum use. A epoxy was able to fulfill this tasks. The evacuation characteristics of the constructed chamber was improved by minimizing the inner surface outgassing rate. Therefore, the throughput outgassing rate test method was used in the comparisons between the selected two aluminum materials (A2017 and A5353) samples short time period (one hour) outgassing rates. Different machining methods and treatments for the inner surface of the vacuum chamber were tested. The machining of the surface of material A (A2017) with ethanol as coolant fluid was able to reduce its outgassing rate a factor of 6 compared with a non-machined sample surface of the same material. The reduction of the surface porous oxide layer on the top of the aluminum surface by the pickling process with HNO3 acid, and the protection of it by producing another passive non-porous oxides layer using anodizing process will protect the surface for longer time and will minimize the outgassing rates even under humid atmosphere The residual gas analyzer (RGA) 6. Summary test shows that more than 85% of the gases inside the test chamber were water vapour (H2O) and the rests are (N2, H2, CO), so liquid nitrogen water vapor trap can enhance the chamber pumping down process. As a result it was possible to construct a chamber that can be pumped down using a turbo molecular pump (450 L/s) to the range of 1x10-6 mbar within one hour of evacuations where the chamber volume is 160 Litters and the inner surface area is 1.6 m2. This is a good base pressure for the process of sputtering deposition of hard thin film coatings. Multilayer thin film coating was deposited to demonstrate that nanostructured thin film within the (Ti, Al, Si) N system could be prepared by reactive magnetron sputtering of multi thin film layers of TiN, AlSiN. The (SNMS) spectrometry of the test samples show that a complete diffusion between the different deposited thin film coating layers in each sample takes place, even at low substrate deposition temperature. The high magnetic flux of the unbalanced magnetrons and the high sputtering power were able to produce a high ion-toatom flux, which give high mobility to the coated atoms. The interactions between the high mobility of the coated atoms and the ion-to-atom flux were sufficient to enhance the diffusion between the different deposited thin layers. It was shown from the XRD patterns for this system that the structure of the formed mixture consists of two phases. One phase is noted as TiN bulk and another detected unknown amorphous phase, which can be SiNx or AlN or a combination of Ti-Al-Si-N. As a result we where able to deposit a nanocomposite coatings by the deposition of multilayers from TiN, AlSiN thin film coatings using the constructed vacuum chamber

Lung cancer, mainly caused by tobacco smoke, is the leading cause of cancer mortality. Large efforts in prevention and cessation have reduced smoking rates in the U.S. and other countries. Nevertheless, since 1990, rates have remained constant and it is believed that most of those currently smoking (~25%) are addicted to nicotine, and therefore are unable to stop smoking. An alternative strategy to reduce lung cancer mortality is the development of chemopreventive mixtures used to reduce cancer risk. Before entering clinical trails, it is crucial to know the efficacy, toxicity and the molecular mechanism by which the active compounds prevent carcinogenesis. 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), N-nitrosonornicotine (NNN) and benzo[a]pyrene (B[a]P) are among the most carcinogenic compounds in tobacco smoke. All have been widely used as model carcinogens and their tumorigenic activities are well established. It is believed that formation of DNA adducts is a crucial step in carcinogenesis. NNK and NNN form 4-hydroxy-1-(3-pyridyl)-1-butanone releasing and methylating adducts, while B[a]P forms B[a]P-tetraol-releasing adducts. Different isothiocyanates (ITCs) are able to prevent NNK-, NNN- or B[a]P-induced tumor formation, but relative little is know about the mechanism of these preventive effects. In this thesis, the influence of different ITCs on adduct formation from NNK plus B[a]P and NNN were evaluated. Using an A/J mouse lung tumor model, it was first shown that the formation of HPB-releasing, O6-mG and B[a]P-tetraol-releasing adducts were not affected when NNK and B[a]P were given individually or in combination, of by gavage. Using the same model, the effects of different mixtures of PEITC and BITC, given by gavage or in the diet, on DNA adduct formation were evaluated. Dietary treatment with phenethyl isothiocyanate (PEITC) or PEITC plus benzyl isothiocyanate (BITC) reduced levels of HPB-releasing adducts by 40*50%. This is consistent with a previously shown 40% inhibition of tumor multiplicity for the same treatment. In the gavage treatments with ITCs it seemed that PEITC reduced HPB-releasing DNA adducts, while levels of BITC counteracted these effects. Levels of O6-mG were minimally affected by any of the treatments. Levels of B[a]P-tetraol releasing adducts were reduced by gavaged PEITC Summary Page XII and BITC, 120 h after the last carcinogen treatment, while dietary treatment had no effects. We then extended our investigation to F-344 rats by using a similar ITC treatment protocol as in the mouse model. NNK was given in the drinking water and B[a]P in diet. Dietary PEITC reduced the formation of HPB-releasing globin and DNA adducts in lung but not in liver, while levels of B[a]P-tetraol-releasing adducts were unaffected. Additionally, the effects of PEITC, 3-phenlypropyl isothiocyanate, and their N-acetylcystein conjugates in diet on adducts from NNN in drinking water were evaluated in rat esophageal DNA and globin. Using a protocol known to inhibit NNNinduced esophageal tumorigenesis, the levels of HPB-releasing adduct levels were unaffected by the ITCs treatment. The observations that dietary PEITC inhibited the formation of HPB-releasing DNA adducts only in mice where the control levels were above 1 fmol/µg DNA and adduct levels in rat lung were reduced to levels seen in liver, lead to the conclusion that in mice and rats, there are at least two activation pathway of NNK. One is PEITC-sensitive and responsible for the high adduct levels in lung and presumably also for higher carcinogenicity of NNK in lung. The other is PEITC-insensitive and responsible for the remaining adduct levels and tumorigenicity. In conclusion, our results demonstrated that the preventive mechanism by which ITCs inhibit carcinogenesis is only in part due to inhibition of DNA adduct formation and that other mechanisms are involved. There is a large body of evidence indicating that induction of apoptosis may be a mechanism by which ITCs prevent tumor formation, but further studies are required.

In this work we present and estimate an explanatory model with a predefined system of explanatory equations, a so called lag dependent model. We present a locally optimal, on blocked neural network based lag estimator and theorems about consistensy. We define the change points in context of lag dependent model, and present a powerfull algorithm for change point detection in high dimensional high dynamical systems. We present a special kind of bootstrap for approximating the distribution of statistics of interest in dependent processes.

Microsystem technology has been a fast evolving field over the last few years. Its ability to handle volumes in the sub-microliter range makes it very interesting for potential application in fields such as biology, medicine and pharmaceutical research. However, the use of micro-fabricated devices for the analysis of liquid biological samples still has to prove its applicability for many particular demands of basic research. This is particularly true for samples consisting of complex protein mixtures. The presented study therefore aimed at evaluating if a commonly used glass-coating technique from the field of micro-fluidic technology can be used to fabricate an analysis system for molecular biology. It was ultimately motivated by the demand to develop a technique that allows the analysis of biological samples at the single-cell level. Gene expression at the transcription level is initiated and regulated by DNA-binding proteins. To fully understand these regulatory processes, it is necessary to monitor the interaction of specific transcription factors with other elements - proteins as well as DNA sites - in living cells. One well-established method to perform such analysis is the Chromatin Immunoprecipitation (CHIP) assay. To map protein-DNA interactions, living cells are treated with formaldehyde in vivo to cross-link DNA-binding proteins to their resident sites. The chromatin is then broken into small fragments, and specific antibodies against the protein of interest are used to immunopurify the chromatin fragments to which those factors are bound. After purification, the associated DNA can be detected and analyzed using Polymerase Chain Reaction (PCR). Current CHIP technology is limited as it needs a relatively large number of cells while there is increasing interest in monitoring DNA-protein interactions in very few, if not single cells. Most notably this is the case in research on early organism development (embryogenesis). To investigate if microsystem technology can be used to analyze DNA-protein complexes from samples containing chromatin from only few cells, a new setup for fluid transport in glass capillaries of 75 µm inner diameter has been developed, forming an array of micro-columns for parallel affinity chromatography. The inner capillary walls were antibody-coated using a silane-based protocol. The remaining surface was made chemically inert by saturating free binding sites with suitable biomolecules. Variations of this protocol have been tested. Furthermore, the sensitivity of the PCR method to detect immunoprecipitated protein-DNA complexes was improved, resulting in the reliable detection of about 100 DNA fragments from chromatin. The aim of the study was to successively decrease the amount of analyzed chromatin in order to investigate the lower limits of this technology in regard to sensitivity and specificity of detection. The Drosophila GAGA transcription factor was used as an established model system. The protein has already been analyzed in several large-scale CHIP experiments and antibodies of excellent specificity are available. The results of the study revealed that this approach is not easily applicable to "real-world" biological samples in regard to volume reduction and specificity. Particularly, material that non-specifically adsorbed to capillary surfaces outweighed the specific antibody-antigen interaction, the system was designed for. It became clear that complex biological structures, such as chromatin-protein compositions, are not as easily accessible by techniques based on chemically modified glass surfaces as pre-purified samples. In the case of the investigated system, it became evident that there is a need for more research that goes beyond the scope of this work. It is necessary to develop novel coatings and materials to prevent non-specific adsorption. In addition to improving existing techniques, fundamentally new concepts, such as microstructures in biocompatible polymers or liquid transport on hydrophobic stripes on planar substrates to minimize surface contact, may also help to advance the miniaturization of biological experiments.