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Pedogenic carbonates in loess formation rates, formation conditions and source apportionment assessed by isotopes and molecular proxies (2011)

Martina Gocke

Interest in secondary (pedogenic) carbonates as an archive for paleoclimatic reconstructions in arid and semiarid regions has increased during recent decades. Their carbon (C) isotope composition represents the conditions prevailing during their formation because they are formed by precipitation of Ca2+ from soil solution with dissolved CO2 from soil air originating from root and rhizomicrobial respiration. Thus, pedogenic carbonates are an important tool for estimation of age of pedogenesis and for reconstruction of the local paleovegetation. Potential reequilibration of pedogenic carbonates with younger soil CO2 can entail loss of chronological and paleoenvironmental information. Although methodological resolution of these studies depends on the time scale of pedogenic carbonate formation and recrystallization, its rates and periods remain unknown. The first objective therefore was the first-time assessment of the time frame of pedogenic CaCO3 formation and recrystallization under controlled conditions. The other aim was to reveal the potential of rhizoliths, a special form of pedogenic carbonates (calcified roots), from a loess-paleosol sequence for paleoenvironmental studies. In loess as a common soil parent material, initial CaCO3 recrystallization rates were successfully determined with the 14C isotopic exchange approach by exposing loess to artificially labeled 14CO2 and subsequent quantification of 14C incorporated in secondary (recrystallized) CaCO3. Within the range of natural soil CO2 concentrations, recrystallization rates increased strongly with CO2 concentration. In further studies, loess was exposed to 14CO2 respired by roots and rhizomicrobial organisms of plants labeled in 14CO2 atmosphere, to estimate the effects of several factors (root vicinity, temperature, accumulation depth) on the recrystallization rate. Rates from planted loess were two orders of magnitude higher than those from unplanted loess, mostly in the range of 10-5 day-1. Significantly higher CaCO3 recrystallization rates in rhizosphere than in loess distant from roots were attributed to three factors: high CO2 concentration from root and rhizomicrobial respiration, low pH caused by release of CO2 and root exudates, and high Ca2+ and HCO3- concentration caused by water uptake by roots. Considerable influence of the latter was demonstrated by low CaCO3 recrystallization rates at low temperatures and vice versa, reflecting the increasing transpirational pull with increasing temperatures. Assuming repeated recrystallization of both primary and secondary CaCO3, extrapolation of initial CaCO3 recrystallization rates showed that at least 102 – 103 years are necessary for complete recrystallization of CaCO3 in ‘root-free’ loess by formation of secondary CaCO3, depending on length of the growing season. Increasing temperature promoted CaCO3 recrystallization rates, but the contrast was compensated for recrystallization periods because of the negative effect of increasing temperature on length of the growing season. In contrast, pedogenic carbonates can form much faster close to roots (101 – 102 years) because of mass flow to the roots leading to rhizolith formation. As a consequence of this wide temporal spectrum of pedogenic carbonate formation, variable methodological resolution has to be considered in paleoenvironmental studies based on stable isotope composition of pedogenic carbonates, depending on climatic factors and formation of carbonate concretions. Rhizoliths, formed by encrustation of roots with secondary CaCO3, yield high potential for paleoenvironmental studies. At the late Pleistocene loess-paleosol sequence of Nussloch, SW Germany, rhizolith CaCO3 was completely secondary and not contaminated by postsegregational alteration. Radiocarbon dating of one rhizolith sample reinforced the assumption of potential postsedimentary formation of rhizoliths. In the investigated profile, stable C isotope composition indicated C3 source vegetation for organic matter (OM) of both loess and rhizoliths, but lipid molecular proxies revealed grass biomass as origin of loess OM, and shrub or tree roots as source of rhizoliths. Moreover, OM in loess adjacent to rhizoliths was considerably contaminated by rhizomicrobial and root remains at least up to a distance of 5 cm. Alteration of loess OM and its isotope composition by postsedimentary penetration of deep-rooting plants might entail uncertainties for paleoenvironmental studies based on loess OM. In summary, the important role of vegetation on pedogenic CaCO3 formation and recrystallization was shown under controlled and field conditions. Plant roots and associated microorganisms have direct influence on these processes, while further factors of pedogenesis like climate exert an indirect effect, but on the long term probably are of greater importance than effects on the rhizosphere scale.

Modulation of Incommensurately Modulated Structures Studied by the Maximum Entropy Method (2011)

Li Liang

In this thesis, modulated properties of incommensurately modulated crystals are studied by the Maximum Entropy Method (MEM). This was done exemplarily on the compounds Rubidium tetrachlorozincate and Chromium pyrophosphate. To do so, the MEM derived (3+1)-dimensional superspace electron density was analysed to receive information on atomic positions and their modulation, and structure refinement by the method of least-squares and interpretation of the difference-Fourier maps were performed to better describe the atomic displacement parameters (ADPs) and to improve the applied structural models. All the MEM calculations are done by the computer program BayMEM. The analysis of this MEM reconstructed density map is done by the computer program EDMA. Our results suggest that the modulation of harmonic ADPs, anharmonic ADPs and its modulation form an intrinsic part of incommensurately modulated structures. We have shown that with a data set of certain resolution and satellite reflections of higher order, the inclusion of modulation of harmonic ADPs, the anharmonic ADPs and the modulation of anharmonic ADPs can significantly improve the fit of the structure model to the diffraction data. Such model then better represents the true nature of the structure under investigation.

Auswirkungen eines Ultralangstreckenlaufs auf ausgewählte physiologische und psychologische Parameter als mögliche Marker von Überbelastungen (2011)

Thomas Bossmann

Problemstellung Überbelastungen stellen ein weit reichendes Problem im Leistungs- und ambitionierten Freizeitsport dar. Allgemein gültige Diagnoseparameter fehlen ebenso wie hinreichend verlässliche Parameter, die frühzeitige Warnhinweise bei zu hohen Belastungsfaktoren geben könnten und in der Trainingssteuerung einsetzbar sind. Für Ultralangstreckenläufer, die häufig mehrtägige Wettkämpfe absolvieren, sind besonders solche Parameter interessant, die sich im Feld und in nicht invasiver Form ermitteln lassen. Methode 6 TN ermittelten während einer Trainingsphase mit normalem Belastungsumfang, während eines 17-tägigen Ultramarathons (Deutschlandlauf) sowie während einer anschließenden Regenerationsphase täglich die morgendliche Ruheherzfrequenz, Parameter der Herzfrequenzvariabilität (HRV) sowie die psychische Befindlichkeit. Für jeden Parameter wurden zunächst Normbereiche festgelegt. Mittels Laktat-Stufentests wurde die maximale Leistungsfähigkeit der Teilnehmer zu drei unterschiedlichen Zeitpunkten ermittelt. Gleichzeitig wurden Diagnoseparameter einer Überbelastung vordefiniert und die Annahme formuliert, dass mindestens dreitägige Auslenkungen einzelner Parameter aus den während der ersten Messphase ermittelten Normwertbereichen dem Auftreten der Diagnoseparameter oder dem Abbruch des Laufs vorausgehen würden (kritische Ereignisse) Ergebnisse Vier der sechs untersuchten Sportler mussten den Lauf frühzeitig abbrechen, bei drei Sportlern wurden diagnoserelevante Veränderungen bezüglich einer Überbelastung dokumentiert. Bei den Abbrechern traten bereits während der Wettkampfphase kritisch erhöhte Ruheherzfrequenzwerte, eine kritisch erniedrigte Herzfrequenzvariabilität sowie eine kritisch verschlechterte Befindlichkeit auf. Die untersuchten Parameter reagierten individuell unterschiedlich, zeigten jedoch bereits frühzeitig Auslenkungen an, die dem Abbruch des Laufs bzw. Diagnoseparametern einer Überbelastung voraus gingen. Alle Teilnehmer zeigten während der Regenerationsphase Veränderungen, die auf eine erhöhte sympathische Aktivität schließen lassen.

Holographic Investigation of Azobenzene-Containing Low-Molecular-Weight Compounds (2011)

Hubert Audorff

In the present thesis, holographic volume and surface relief gratings in azobenzene-containing low-molecular-weight compounds are investigated to obtain a broader understanding of this new class of material. Azobenzene chromophores undergo light-induced trans-cis-trans isomerization cycles leading to a reorientation of the long axis of the chromophores. If linearly polarized light is incident on the sample, these isomerizations result in a reorientation of this axis perpendicular to the light polarization. A holographic light grating, which can be formed by the interference of two coherent laser beams, leads to the inscription of a refractive-index modulation in the material. The azobenzene-containing low-molecular-weight compounds studied in this thesis consist of different building blocks: the core unit, the azobenzene chromophores with substituents, and the spacer and the linkage group between chromophore and core unit. These components can be used in a modular-design principle to synthesize a large library of low-molecular-weight compounds. Surprisingly, some of the investigated low-molecular-weight compounds form also a liquid-crystalline phase besides the amorphous phase as evidenced by polarized microscopy. If these liquid-crystalline compounds are prepared as solid films, however, they are quenched to an amorphous state. Upon reorientation of the azobenzene chromophores by illumination with a holographic light grating, a phase transition from the amorphous to an ordered state can be induced. This phase change in the latent liquid-crystalline low-molecular-weight compounds is very interesting for applications. The latent liquid-crystalline low-molecular-weight compounds show a post-development of the refractive-index modulation after the writing process. The holographic gratings are even stable at temperatures higher than the glass transition temperature, which further proves the light-induced formation of an ordered domain. In contrast to their polymeric counterparts, molecular materials are expected to show a faster response to light because of the absence of polymer chain entanglements. Therefore, molecular glasses can be used as blending material for photo-addressable polymers to improve the photo-sensitivity of the blend as compared to the pure polymer. The influence of the core and the substituent was investigated in low-molecular-weight compounds which do not form liquid-crystalline phases. An azobenzene-containing diblock copolymer for holographic data storage consists of an inert majority block and a minority block containing the covalently bound photo-sensitive azobenzene chromophores. Blending a few weight percent of the optimized molecular glass to the diblock copolymer leads to an increase of sensitivity with increasing content of the molecular glass, mainly because the writing time to the maximum of the refractive-index modulation decreased. The increase of the sensitivity is much larger than the observed rise of the refractive-index modulation due to the higher concentration of azobenzene chromophores. It was demonstrated that the shorter writing times are not caused by thermal effects, the molecules of the molecular glass in the inert block, or by changes of the free volume or the morphology, but that they are due to the azobenzene chromophores of the molecular glass in the minority block. They reorient faster than the chromophores attached to the polymer backbone and, thereby create free volume. Additionally, they can assist the reorientation of the azobenzene chromophores bound to the polymer by cooperative effects, i.e. dipolar and steric interactions. Both effects result in shorter writing time and higher sensitivity of the system. In a blend containing two weight percent of the molecular glass, the inscribed gratings are still long-term stable and the sensitivity increases by a factor of 1.7 as compared to the pure diblock copolymer. Upon illumination of an azobenzene-containing material with a holographic light grating, besides the volume grating, also a surface relief grating can develop. Surface modulations with heights of up to 600 nm were achieved in molecular glasses. It was found that the build-up of the surface relief grating depends on the electrical susceptibility of the material at the optical frequency of the laser and the polarization of the laser beams. These experimental findings are in agreement with the gradient force model. According to this theory, the macroscopic material transport results from the forces on the polarized material in the electrical field gradient caused by the holographic light grating. For many applications it is important that the holographically produced surface relief gratings can be transferred to polymer surfaces. Replica molding can be used to easily copy the surface modulations to e.g. polycarbonate.

Development of Bacillus subtilis spores and cells for surface display of proteins (2011)

Quynh Anh Nguyen

Surface display has attracted the attention of researchers in developing efficient display systems expressing heterologous polypeptides on the surface of bioparticles such as phages, bacterial and eukaryotic cells and bacterial spores. Among these bioparticles, the endospore from B. subtilis has advantages, including feasibility of production, safety feature, the robustness of the bacterial spore allowing storage in the desiccated form, a technological platform supported by extensive tools for genetic manipulation and less size restrictions of the displayed proteins compared to cell- and phage-based systems. A strategy to engineer B. subtilis spores to display heterologous protein on their surface is to use outer spore coat proteins (CotB, CotC, CotG) or an inner-coat protein (OxdD) with the coat genes’ transcriptional and translational signals as carriers (Isticato et al., 2001; Mauriello et al., 2004; Hinc et al., 2010; Zhou et al., 2008a; Potot et al., 2010; Kim et al., 2005a; Kwon et al., 2007). This strategy guarantees the timing for fusion protein synthesis during coat formation, but the amount of produced fusion proteins cannot be controlled. Therefore, the first aim of this doctoral thesis focused on construction of more effective expression systems for spore surface protein anchoring. A novel approach of substitution of native promoter by two different IPTG-inducible promoters to the increase the production of fusion protein is presented here. CotB was used and the expression of the cotB gene was regulated by either its own promoter, the Pgrac and the PSgrac promoter in a series of plasmids which can be integrated into or replicated independently of the B. subtilis chromosomal DNA. Two reporter proteins, α-amylase Q from B. amyloliquefaciens (AmyQ) (Palva, 1982) and GFPuv – an enhanced version from the GFP protein of the jellyfish Aequorea victoria (Crameri et al., 1996), were fused downstream of the CotB protein. To assess the enhancement of GFPuv displayed on the spore surface, CotC and CotG were similarly examined. The results indicated that the Pgrac promoter is a suitable, hence recommended as a promoter of choice. Substitution of the native promoter by Pgrac promoter, the amount of proteins displayed per spore can be increased two-fold. Furthermore, the display of heterologous proteins on the spore surface when using different carriers is gene dosage dependent. And for the first time, the tendency of the three Cot proteins’ localization on the spore coat compartment is reported using the GFPuv tag. Second, a new B. subtilis spore-based system for protein expression and purification was developed. Using this system, proteins prone to form inclusion bodies can be anchored on the spore surface, separated by a mini-intein derived from the SSp DnaB, which was then used as self-cleaving tag for purification by shifting the pH and/or temperature conditions, with no addition of any proteases or thiol reagent (Mathys et al., 1999). To construct the system, the mini-intein was fused downstream of the CotB protein, followed by the reporter protein AmyQ. By changing the pH of the buffer, the mini-intein self-cleaving process was induced followed by the release of α-amylase into the supernatants. This observation suggests the use of the B. subtilis spores as an effective and low cost tool for protein purification. However, concerns related to premature of the pH-inducible mini-intein and auto-release of coat protein raise the question about the stability of the fusion coat-heterologous protein on the spore surface using the system. Hence, further investigation is needed to achieve a usable spore-based purification system. The last aim of the thesis was to apply the newly constructed B. subtilis spore display and the cell surface display systems (Nguyen and Schumann, 2006) to generate cellulose chips, in which enzymes were immobilized on the surface of microorganism cells or spores. The cellulase A (CelA) from C. thermocellum (Beguin et al., 1985) was utilized as a model enzyme. Unfortunately, the results showed an ineffective anchoring of CelA on the cell wall. This indicates the unsuccessful creation of cell-based cellulase chip when using the SrtA transpeptidase. In contrast, CelA was verified to be successfully displayed on the spore surface using CotB and CotG, but not CotC, as carriers. In general, a large volume of culture (up to one liter) must be prepared containing both cells and spores displaying CelA on the surface to assure sufficient CMC degradation. This might indicate a low activity of CelA. Further works should be done in selection of cellulase and improvement of the systems to generate the more effective cellulase chips.

Dynamics and statistics of hydrodynamically interacting particles in laminar flows (2011)

Jochen Bammert

The subject of this thesis is the investigation of the dynamics and statistics of hydrodynamically interacting particles in low Reynolds number flows, which is discussed in three interrelated themes. The first theme focuses on polymer fractionation. With our basic model we explore the possibility to sort dumbbells with respect to their size using a two dimensional periodic potential. It turns out that the purely diffusive behavior of a dumbbell in this structured landscape is dominated by the ratio of two characteristic length scales, namely the wavelength of the potential l and the size of the dumbbell b. We explain why the diffusion constant in the potential plane shows a pronounced local maximum around l/b equal 3/2. Furthermore, the influence of the spring rigidity and the hydrodynamic interaction on the diffusive motion are examined as well as the dumbbell statistics. If the dumbbell is driven by an external flow through the periodic landscape two different kinds of motion occur: transport along a potential valley and a stair-like motion oblique to the trenches. In the latter case, the dumbbell jumps regularly to a neighboring valley which results in an effective deflection. The onset of the oblique movement as well as the deflection angle beta depend on the hydrodynamic interaction, on the ratio l/b, and on the Brownian motion of the beads. Especially the significant dependence of beta on l/b enables particle sorting. The results are published. The second theme deals with the Brownian dynamics in shear flows. Here, we investigate the correlations of particle fluctuations in order to characterize the direct interplay between thermal motion, hydrodynamic interactions, and non-uniform flows.With respect to the experimental implementation the particles are caught by harmonic potentials. First, we consider one trapped Brownian bead in linear shear and Poiseuille flows. The correlation functions of the particle’s position and velocity fluctuations are calculated analytically. The main result is the occurrence of shear-induced cross-correlations between orthogonal fluctuations in the shear plane which are asymmetric in time. Moreover, the positional probability distribution, P(r), of a single bead in both types of flow is determined. In Poiseuille flow, where no analytical solutions can be obtained, we use perturbation expansions to derive formulas for P(r) that are valuable for the analysis of experimental data. In the case of a linear shear flow, a connection between the static correlations and the distribution functions is derived which allows a consistency check between independent measurements. Considering a system with several Brownian particles it is obvious that hydrodynamic interactions influence the correlations. In order to investigate this effect, we calculate the positional correlation functions for a setup of two trapped Brownian beads which are exposed to a linear shear flow. As expected, the one-particle correlations change compared to the single particle case described above. They depend on the distance between the two beads. In addition, we find inter-particle correlations between orthogonal positional fluctuations of different particles. The structure of these new cross-correlations depends significantly on the relative orientation of the two beads in the shear flow. They can have zero, one, or two local extrema as a function of time. In collaboration with Prof. Wagner from Saarbrücken some of our predictions are already confirmed by experiments, where polystyrene beads are caught by optical traps and simultaneously exposed to linear shear flows in a special microfluidic device. The results are published and further investigations are in progress.The third theme concentrates on the rheology of colloidal suspensions. Our deterministic model system consists of Hookean dumbbells suspended in a confined Newtonian fluid under constant shear. We perform a numerical study using fluid particle dynamics simulations, where the effective viscosity of the suspension, eta, and the dumbbell statistics are determined. The investigations on the tumbling motion of a single dumbbell reveals that eta is influenced by three different contributions: the volume fraction occupied by the dumbbell, the hydrodynamic interaction between the beads, and elastic correlation effects. For a suspension of independent spheres we observe in our simulations that the viscosity, as a function of the volume fraction Phi, differs from the prediction of Einstein, Batchelor and Green if Phi becomes larger than 8%. Replacing the beads by dumbbells leads to an increase of eta , which depends significantly on the length of the springs connecting the two beads. The distribution function for the orientation angle of the dumbbells indicates the complex motion of the individual objects in the suspension, which may lead to the so-called elastic turbulence, as experimentally discovered by Groisman and Steinberg.

Klassifikation gewisser Darstellungen halbeinfacher Liealgebren (2011)

Ridvan Güner

Zusammenfassung Die Arbeit behandelt folgende Fragen aus der Darstellungs- und Invariantentheorie halbeinfacher Liealgebren: Gegeben eine halbeinfache (meist: eine einfache) komplexe endlich dimensionale Liealgebra L . Betrachtet wird das Monoid M = M(L) der Äquivalenzklassen der endlich dimensionalen irreduziblen komplexen Darstellungen von L . M wird identifiziert mit dem Gitter der entsprechenden höchsten Gewichte (bezüglich einer ausgewählten Cartanalgebra von L und einer ausgewählten Basis der zugehörigen Wurzeln). Diese Identifizierung liefert die Monoidstruktur von M . Zu einer Darstellung pi von L kann man die symmetrische Algebra von pi betrachten (als unendlich dimensionale Darstellung, welche die symmetrischen Potenzen von pi als endlich dimensionale direkte Summanden enthält.) Ein höchstes Gewicht von L , das als höchstes Gewicht einer irreduziblen Komponente in einer n-ten symmetrischen Potenz von pi auftritt, sei gutes dominantes Gewicht genannt. Die Menge aller guten dominanten Gewichte bildet ein Untermonoid M(pi) des Monoids M . Solch ein M(pi) besitzt einen natürlich definierten Rang r(pi) , der größer-gleich 1 und kleiner-gleich r ist. (S. Seite 8 der Arbeit in der Einleitung.) Hier ist r der Rang von L , d.h. die Dimension einer Cartanunteralgebra von L . Nun: Eine Darstellung pi von L sei gut genannt, wenn r(pi) kleiner als r ist, und schlecht, wenn r(pi) gleich r ist. In den Paragraphen 4 und 5 der Arbeit werden dann - explizit als L-Darstellungen - die n-ten symmetrischen Potenzen der guten Darstellungen pi beschrieben. Im ersten Paragraphen der Arbeit wird nachgewiesen, dass Darstellungen bis auf wenige Ausnahmen schlecht sind, und es werden Listen von schlechten Darstellungen verifiziert. Letztlich werden die Typen der einfachen Liealgebren - die vier klassischen Reihen und die fünf Ausnahmealgebren - einzeln und individuell abgehandelt. In diesem ersten Paragraphen der Arbeit werden, wie auch später, entscheidend explizite Ausreduzierungen von symmetrischen Potenzen von Darstellungen benutzt, die in ausführlichen Listen zusammengestellt sind, s. Liste 1 und Liste 2 am Ende der Arbeit. (Die Berechnungen wurden mit dem Lie-Berechnungspaket aus [van Leeuwen] gemacht. In Einzelfällen werden auch explizite Ausreduzierungssätze benutzt, weil versucht wird, bei den Beweisen Argumente aus der Darstellungstheorie zu bevorzugen. Gemäß dem ersten Paragraphen sind für die einzelnen Typen einfacher Liealgebren fast alle irreduziblen Darstellungen schlecht. Bei jedem Typ bleibt nur eine kurze Liste von möglicherweise guten Darstellungen übrig. In Paragraph 2 werden nun die Darstellungen in diesen Restlisten als tatsächlich gut nachgewiesen. Paragraph 3 gibt eine Zusammenfassung der guten Darstellung unter einem anderen Gesichtspunkt: Die guten Darstellungen sind geordnet nach ihrem Rang (und nicht nach dem Isomorphietyp der Liealgebra ). In den Paragraphen 4 und 5 wird - für alle guten irreduziblen Darstellungen pi - die genaue Struktur (als vollständig reduzible Darstellung) der symmetrischen Potenzen von pi bestimmt. Benutzt wird dabei auch detailliertere Invariantentheorie und die Kenntnis von Hauptisotropiegruppen bei Darstellungsräumen.

Ordering of Nanoparticles by Wrinkle-Assisted Self-Assembly : Controlling Plasmonic Coupling Effects (2011)

Alexandra Schweikart

Structures of spatial scale between 10Å and 1000Å are known as nanomaterials and have attracted immense interest over the last decades (Nobel Prize in physics in 2010 was awarded for the nanomaterial graphene). Materials within this scale show a large surface-to-volume ratio and amplify surface-related properties. Governing and manipulating material on this almost atomic level is one of the most active fields in modern natural science. Nanoscale technology, such as some of the processes involved in steel production and painting, has been empirically utilized in human society for centuries, however, a scientific investigation of phenomena on this spatial scale only began in 1857 when Michael Faraday reported on the synthesis and colors of gold colloids. In 1959 interest in the nanoscale was stimulated by an American physicist, Richard Feynman, in his famous “There’s plenty of room at the bottom” address, and the term nanotechnology first appeared in 1974 from the Japanese Norio Tanigucho. Since these pioneering works, thousands of publications have been focused on the synthesis, modification, properties and assembly of nanoparticles. Great progress has been attained in the preparation of nanoparticles of any desired size, shape and composition. Metal nanoparticles are particularly attractive due to their spectacular size and shape dependent optical and electronic properties. Color variations of nanoparticle suspension for example arise from changes in the composition, size and shape of nanoparticles, as well as from the proximity of other metal nanoparticles. The average distances of nanoparticles in thin films influence the spectral features because of inter-nanoparticle coupling. These effects are often the result of changes in the so-called surface Plasmon resonance, the frequency at which conduction electrons oscillate in response to the alternating electric field. Provided nanoparticles form ordered arrays, they can additionally have unique and fascinating optical properties because of photonic band gap effects with potential applications such as detectors, circuits, light sources, polymeric opals or meta-materials. The present work deals with the controlled placement of nanoparticles by physical con-straints. Exact placement of nanoparticles allows for the control of the inter-nanoparticle distance and thus determines the coupling effects (here: Plasmon coupling) which arise upon interaction with electromagnetic radiation. Different coupling leads to different distance-dependent signals and such substrates can serve as sensors if, for example, Raman spectroscopy is carried out for detection of the signal. Currently, most templates are created using lithographic techniques. Particularly if structures on the sub-micron scale are desired, electron beam lithography has to be used which involves environmentally harmful etching processes. Within this work we show how controlled wrinkling of a thin rigid film on a soft, elastomeric substrate, can be used as an alternative to fabricate nano-templates without using any lithography. As a substrate, a silicon elastomer poly (dimethylsiloxane) (PDMS) was used. Upon stretching such substrates uniaxially, an enlarged surface was exposed to oxygen plasma and converted to silica by oxidation. After releasing the strain, periodic wrinkles appeared perpendicular to the applied strain. Under defined conditions, such wrinkles have a regular sinusoidal topology featuring a single dominant wavelength and amplitude. The formation process could easily be tuned by tuning the plasma exposure to generate periodically structured templates between few hundreds of nanometers and several microns. In this work, wrinkled templates were tailored such that suitably sized nanoparticles could be arbitrarily assembled into a hierarchical structure by drying colloids out of suspension in a channel-like confinement offered by wrinkles in contact with a flat substrate. Using the same template geometry (same wavelength and amplitude of wrinkles) but different particle concentration of spherical polystyrene beads (r = 55nm) we found parallel particle-structures ranging from single parallel lines at low particle concentration to dense prismatic ridges at high particle concentration. The wavelength of the wrinkled template defined the spacing between the particle lines. Moreover, we performed Monte Carlo (MC) computer simulations in collaboration with the theoretical physics department (Prof. Dr. Matthias Schmidt and Dr. Andrea Fortini) at the Uni-versity of Bayreuth to assess the dominant driving forces during the assembly process. Be using MC, colloidal particle assemblies can be characterized in terms of their equilibrium configuration that minimizes the free energy. Simulations were performed on particles in a box delimited by a flat hard wall and a sinusoidal hard wall according to our experimental system. These simulations precisely predicted the exact assembled geometry in thermal equilibrium. Comparing results of simulation and experiment we found perfect agreement between the equilibrium structures. We discovered the confinement itself to be mainly responsible for the assembled morphology of nanoparticle, which makes the process independent of the detailed chemistry of particles. In addition we obtained very similar structures with the same assembly strategy but using gold nanoparticles (r = 33 nm) instead of polymeric particles. We fabricated lines of gold nanoparticles assembled in a single file and lines two particles wide using similar particle concentration but different sizes of the confinement template. The different morphologies of the lines give rise to different optical signals as collective oscillation of conduction electrons result in different interaction with electromagnetic radiation. Surface Plasmon resonance due to Plasmon coupling between adjacent particles arises. Different morphology-dependent signals of nanoparticles in contact within the lines were detected by surface enhanced Raman spectroscopy (SERS). The electromagnetic field was measured to be randomly distributed along the particle lines with strong enhancements at so-called hot spots located at gaps between neighboring nano-particles. To confirm the measured signal we compared theoretical simulations using the finite-difference time-domain (FDTD) method and experimentally measured dark-field spectroscopy signal along differently shaped lines of particles within a collaboration with Weihai Ni and Dr. Ramón Alvarez-Puebla at the University of Vigo in Spain. Good agreement between theory and experiment indicated that indeed plasmonic coupling of the individual nanoparticles is responsible for the observed SERS effects: Using wrinkle-assisted self-assembly it is possible to control the organization of the colloidal particles on the substrate, with a consequent control over the formation of hot spots and the resulting SERS intensity. Such ordered multiplicities of hot spots give rise to quantitative SERS signals with high sensitivity which has applications as diverse as biological detectors, optical filters and sensors. In addition, this work deals with chemical modification of the wrinkled structure to render it accessible to different solvents as PDMS tends to swell in organic solvents and suffers from poor mechanical stability. Additionally, wrinkles fabricated through a buckling instability of a stiff supported layer under compression are not tension free on the microscopic level and suffer from relaxation on a longer time scale. We introduce in this work two different methods to replicate wrinkles by molding. In micro thermoforming, the wrinkled surface was used as a mold (or caliber) to structure different kinds of polymers (polystyrene and poly (methylmethacrylate)) by pressing the originally wrinkled structure onto a ductile material which preserves the nanostructure after curing. The second methodology was carried out in collaboration with PD. Dr. Kerstin Koch and Michael Bennemann at the Nees institute in Bonn and employed a two-step molding process, where wrinkles were molded against wax and in a second step, the structured wax was cast against epoxy resin. Both methods revealed perfect copies of the wrinkled original with high fidelity even at dimensions as small as a few hundred nanometers and hold no residual stresses because there is only one component. Wrinkles made of tough polymers are now accessible to various solvents which make them potential substrates for microfluidics. In the last part of this work, wrinkles are used as stamps in so-called micro contact printing (µCP). In this technique, a structured elastomeric stamp is used to transfer a surface-active molecule out of solution to a flat substrate by mechanical contact. Patterns of different charge density can be created which have applications in the field of biosensors, diagnostic immunoassays and cell culturing. Traditionally, stamps for µCP are prepared by a two step process where a lithographically fabricated structured silicon master serves as mold. An elastomeric polymer is cast against the caliber and preserves the structure after curing and detaching. As already mentioned lithography is expensive and involves environmentally harmful etching processes. Within this work we introduce the one step wrinkling process to fabricate structured stamps. Even though the diversity of stamp geometries created by wrinkling is limited, the simplicity compared to lithographic techniques is evident. The process of wrinkle formation includes plasma oxidation, which renders the topmost surface hydrophilic. Therefore, charged macromolecules out of aqueous solution were adsorbed onto the surface. The coated relief structure was used as a stamp to transfer the molecules selectively from the elevated parts of the wrinkles to another flat, oppositely charged surface by means of µCP. The topography of the resulting pattern was characterized by Atomic Force Microscopy (AFM) imaging as alternating charged pattern of printed (elevated) and non-printed areas. By varying the geometry of the wrinkled stamp (amplitude and wavelength) we studied the limits in which successful µCP with wrinkles can be carried out. We found the limits for wavelength of the wrinkles below 355nm and amplitudes below 40nm at which the printed structure disappeared because material was transferred from the wrinkles’ hills as well as from the bottom parts. The height of the transferred structure increase with increasing wavelength and amplitude of the wrinkles but tended to a limit of 6-7nm, even though the topology of the stamp increases. The smallest structure found in lateral dimensions was as small as 50nm, appearing as areas where no material was transferred.

Homogen und heterogen katalysierte Dimerisierungsreaktionen von Olefinen (2011)

Tanja Englmann

Ziel der vorliegenden Arbeit war der Einsatz von Übergangsmetallkomplexen als homogene und heterogene Katalysatoren für die Dimerisierung von 1-Penten und 1-Hexen. Weiterhin sollten verschiedene Einflussfaktoren auf die Aktivitäten und Selektivitäten der Dimerisierungsreaktionen ermittelt und optimiert werden. Hierzu wurden Di(imino)pyridin-Übergangsmetallkomplexe synthetisiert und bei homogenen Dimerisierungsreaktionen eingesetzt. Die Synthese der Di(imino)pyridin-Ligandvorstufen verlief über eine Kondensationsreaktion von Diacetylpyridin und unterschiedlich substituierten Anilinen. Mit den hieraus gewonnenen Verbindungen wurden mit Salzen der 3d-Übergangs-metalle die entsprechenden Komplexe synthetisiert. Bei der Variation des Zentralmetalls erzielte der Di(imino)pyridin-Eisen(III)komplex nach Aktivierung mit MAO bei der Dimerisierung von 1-Hexen die besten Ergebnisse. Die in para-Position des Anilinringes halogenierten Di(imino)pyridin-Eisen(III)komplexe lieferten die höchsten Aktivitäten sowohl bei der Dimerisierung von 1-Hexen, als auch bei Kupplungsreaktionen von 1-Hexen mit 1-Penten. Die Selektivitäten für Dimere lagen bei allen Di(imino)pyridin-Eisen(III)komplexen mit substituierten Iminophenylringen um 90%. Neben linearen Produkten wurden auch methyl-verzweigte Alkene gaschromatographisch detektiert. Die Produktverteilungen der Codimerisierungen weisen Ähnlichkeit zur Binomialverteilung auf. Das bedeutet, dass überwiegend Undecene sowie Hexa- und Heptadecene, also „Co-Produkte“, gebildet wurden. Bei allen Produktzusammensetzungen wurde ein geringfügig höherer Anteil an Hexen-Dimeren festgestellt, was bedeutet, dass die Insertion von 1-Hexen etwas schneller erfolgt, als die von 1-Penten. Mit neun verschiedenen Metallocenkomplexen konnte 1-Penten bzw. 1-Hexen mit Selektivitäten über 90% erfolgreich homogen dimerisiert werden. Die Produkt-verteilung bei der Codimerisierung von 1-Penten mit 1-Hexen zeigte ein binomiales Verhalten, wobei in allen Fällen überwiegend „Co-Produkte“ gebildet wurden. So liegen die Dimere im Verhältnis 1:2:1 (C10:C11:C12) vor, während sich für die Trimere (Pentadecene bis Octadecene) ein Verhältnis von 1:3:3:1 ergibt. Im Gegensatz zu den Di(imino)pyridin-Komplex-katalysierten Reaktionen wurden mit Metallocenkomplexen ausschließlich lineare Produkte erhalten. Bei Variation des Verhältnisses der 1-Penten/1-Hexen-Mischung verschob sich die Binomial-Verteilung erwartungsgemäß auf die Seite der Produkte des höher konzentrierten Monomers. Auch unter der Verwendung von methyl-verzweigten Olefinen konnte die binomiale Produktverteilung beobachtet werden. Allerdings konnten mit internen Alkenen keine Umsätze erzielt werden. Ebenso negativ verlief die Aktivierung von Olefinen, die eine Methylgruppe in β-Position besitzen. Sterisch gehinderte Alkene mit tert-Butylgruppen oder neo-Pentylgruppen zeigten ebenfalls keine Tendenz zur Dimerisierung. Durch Zugabe geeigneter Additive, wie Tributylphosphan oder Aluminium-Pulver konnte die Selektivität für Dimere und damit der Anteil der Undecen-Fraktion bei der Codimerisierung von 1-Penten mit 1-Hexen ebenso verbessert werden, wie die Aktivität. Zur Übertragung dieser homogenen Katalyse auf ein heterogenes System wurden 40 heterogene Katalysatoren mit Cp2ZrCl2 hergestellt. Unter Verwendung von SiO2, Al2O3, SiO2/Al2O3, Zeolithen und MCM-41 konnte gezeigt werden, dass das Trägermaterial großen Einfluss auf die Aktivitäten bei der Dimerisierung von 1-Hexen besitzt. Die besten Ergebnisse hinsichtlich der Aktivität (TON = 2934) erzielten die Silicagele, während unter Verwendung von MCM-41 die beste Dimeren-Selektivität erhalten wurde. Die Beladung des Trägers, die Aktivierung durch den Cokatalysator, sowie die WHSV spielten eine große Rolle bei der Selektivität der gebildeten Produkte. Somit konnte nach der Optimierung dieser Parameter der Produktanteil der Hexen-Dimeren wesentlich verbessert werden. Im Vergleich zur homogenen Variante konnten bei der heterogenen Codimerisierung von 1-Penten und 1-Hexen mit aktiviertem Zirkonocendichlorid höhere Selektivitäten für (Co-)Dimere als auch höhere Aktivitäten erzielt werden.

Temporale Fuzzy Logik - Eine Vereinigung der Temporal-Logik und Fuzzy-Logik anhand von vorausschauenden Wartungs- und Überwachungssystemen (2011)

Thorsten W. Schmidt

Fuzzy-Logik und ihre Anwendung in Fuzzy-Reglern ist seit vielen Jahren ein Forschungsthema. In den vergangenen Jahren kamen Fuzzy-Regler vielfach in den verschiedensten industriellen Anwendungen zum Einsatz. Fuzzy-Regler können in Waschmaschinen und anderen Haushaltsgeräten Verwendung finden. Aber der wichtigste Vorteil von Fuzzy-Logik ist die Tatsache, dass das vorhandene Wissen über die Kontrolle eines Prozesses einfach und intuitiv für einen Regler umgesetzt werden kann. Außerdem ist es einfach, einen solchen Regler zu warten oder zu erweitern. Bei Fuzzy-Logik werden Informationen über eine Prozess-Steuerung in einer transparenten Regel-Datenbank abgelegt. Dadurch geht dieses Wissen nie verloren. Allerdings können diese Fuzzy-Regler nicht in bestimmten Anwendungen (zum Beispiel Wartungssystemen) verwendet werden, da sie nicht in der Lage sind, zeitliche Abhängigkeiten zu modellieren, welche wesentlich für diese Systeme sind. Deshalb wird ein neues Konzept zur zeitlichen Fuzzy-Regelung eingeführt, indem Fuzzy-Logik durch neue Prädikate erweitert wird. Diese Prädikate behandeln zeitliche Aspekte, um zu erkennen oder vorherzusagen, wie das vergangene oder zukünftige Verhalten eines Prozesses ist. Mit der Fähigkeit ausgestattet, vergangenes oder zukünftiges Prozessverhalten zu analysieren, kann der Nutzer des so genannten Temporalen-Fuzzy-Reglers leichter Expertenwissen in die Regelung integrieren. Als Beispiele für die Richtigkeit dieses Konzeptes untersucht diese Arbeit das Verhalten eines Fuzzy geregelten Büroraum-Beleuchtungssystems und eines Fuzzy-Video-Verarbeitungs-Tools. Dies verdeutlicht die einfache Handhabung und hohe Effizienz dieses Ansatzes. In dieser Arbeit wird gezeigt, dass es möglich ist, Fuzzy-Logik mit zeitlichen Prädikaten zu erweitern, um die so genannte Temporale-Fuzzy-Logik zu erhalten, welche die Modellierung zeitlicher Abhängigkeiten von Ereignissen ermöglicht. Die Arbeit beschreibt die mathematischen Grundlagen der hier eingeführten zeitlichen Fuzzy-Prädikate. Die zeitlichen Fuzzy-Prädikate sind abgeleitet aus den in sich abgeschlossenen Prädikaten der Temporal-Logik. Wie in der Temporal-Logik ist es dann auch in der Temporalen-Fuzzy-Logik möglich, Bedingungen für komplette Zeitintervalle zu erstellen. So sind die temporalen Fuzzy-Prädikate ebenfalls in sich abgeschlossen. Es ist möglich, zeitliche Abhängigkeiten mit AND und OR verknüpften Prädikaten zu bilden, um mit diesen temporale Regelbedingungen zu formulieren. Die Konjunktion der Prädikate wird wie jede andere Fuzzy-Verknüpfung berechnet. Weiterhin gilt die s- und t-Norm (Funktionen mit den folgenden Bedingungen: Einselement, Monotonie, Kommutativität, Assoziativität) für diese Berechnungen. Solche Fuzzy-Regler können für die Überwachung und Wartung von Anwendungen eingesetzt werden. Dieser Ansatz wird in einem Wartungs-Beispiel gezeigt, in welchem ein Benutzer über defekte Lampen informiert und die Büroraumhelligkeit bei einem gewünschten Niveau gehalten wird. Ein weiterer Anwendungsfall ist die Fuzzy-Videoverarbeitung. Videos können mit hoher Effizienz verarbeitet werden und die Regeln, welche die Videoverarbeitung beschreiben, sind so einfach wie Standard Mamdani-Regeln.

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