Bayreuther Graduiertenschule für Mathematik und Naturwissenschaften (BayNAT)
Mesostrukturierte Metalloxide und Polyoxometallate mittels Ionogener Diblockcopolymere - Synthese, Charakterisierung und Anwendung
- Das Ziel der vorliegenden Arbeit war es, Metalloxide und Polyoxometallate auf der Mesoebene mittels ionogener Diblockcopolymere zu strukturieren, zu charakterisieren und anwendungsspezifisch zu testen. Dabei wurden vor allem drei bisher bekannte Probleme, die mit der Mesostrukturierung von Metalloxiden einhergehen, umgangen.
Zum einen führt die schnelle Hydrolyse und Kondensation reaktiver Metallalkoxid-Precursoren zu unstrukturierbar großen Molekülen. Zum anderen ist oftmals ein direkter Zugang zu der gewünschten Morphologie aufgrund der mizellaren Dynamik des Templates, die von äußeren Einflüssen, wie pH-Wert, Konzentration oder Salzkonzentration abhängt, erschwert. Das dritte Problem ist die schlechte Anbindung des anorganischen Precursors an das organische Templat, was auf schwache, attraktive Wechselwirkungen zwischen beiden Materialien zurückzuführen ist. Generell müssen Hydrolyse, Kondensation und Hybridbildung zwingend synchron ablaufen, um eine Makrophasenseparation zuverlässig zu vermeiden.
Um diese Makrophasenseparation zu vermeiden, wurde am Lehrstuhl AC I ein neuartiges Konzept entwickelt, in dem alle drei Probleme adressiert und gelöst werden konnten. Diese Lösungsansätze werden nachfolgend entsprechend ihrer oben aufgeführten Reihenfolge erklärt. Zunächst wurden anionische oligomere Cluster oder pre-synthetisierte Kolloide als anorganische Precursoren verwendet, anstelle schnell hydrolyisierender und kondensierender Metallalkoxide. Die Cluster besetzen energetische Minima auf dem Weg zu ausgedehnten Oxidstrukturen und neigen somit nicht zur Kondensation. Weiterhin konnte mit 1-dimensionalen kernquervernetzten Polymerbürsten die mizellare Dynamik umgangen werden, da die rigiden zylindrischen Polymerbürsten invariant gegenüber äußeren Einflüssen sind. Außerdem besitzen diese 1-dimensionalen Nanoobjekte ionisierbare Seitenarme, welche einfach protoniert werden können und somit über starke Coulomb-Wechselwirkungen eine stabile Anbindung der anorganischen Oxide an das organische Templat gewährleisten.
Dieses Konzept der ladungsinduzierten Mesostrukturierung mittels molekularer oxidischer Precursoren wurde innerhalb dieser Doktorarbeit weitergeführt, deren Ergebnisse nachfolgend kurz dargestellt werden.
Zuerst wurde am Beispiel von pre-synthetisierten Rutil- und Anatas-Kolloiden gezeigt, dass nicht nur anionische oligomere Cluster, sondern auch Kolloide in 1-dimensionale Poylmerstrukturen eingelagert werden können. Die Kristallstruktur von Rutil und Anatas konnte durch Verwendung unterschiedlicher Säuren (HCl: Rutil; Essigsäure: Anatas) bei der Hydrolyse des Titanalkoxid-Precursors gezielt eingestellt werden. Diese TiO2-Polymorphe besitzen bei niedrigen pH-Werten eine positive Oberflächenladung. Polystyrolsulfonsäure-block-polyallylmethacrylat (PSS-b-PAMA) wurde in Zusammenarbeit mit dem Lehrstuhl MCII als zylindrischer anionischer Antagonist synthetisiert. Die PSS-Seitenarme sind selbst bei niedrigen pH-Werten noch negativ geladen. Die resultierenden 1-dimensionalen Hybridmaterialien besaßen dieselbe Kristallstruktur wie der Precursor, eine homogene Verteilung der Nanopartikel in der Polymermatrix und nach Trocknung eine verschlaufte, sphaghetti-ähnliche Mikrostruktur mit relativ hoher spezifischer Oberfläche.
In einer detaillierteren Studie wurde zusätzlich der Einfluss der Länge der zylindrischen Template auf die Packung der 1-dimensionalen Nanoobjekte und auf die daraus resultierende spezifische Oberfläche untersucht. Dabei wurden zylindrische Hybridmaterialien aus Heteropolysäuren des Keggin-Typ Polyoxometallates (Keggin POM), die in 1-dimensionale Polybutadien-block-poly(2-vinylpyridin) (PB-b-P2VP) Polymerbürsten eingelagert wurden, verwendet. Hierbei zeigte sich insbesondere, dass eine kurze Ultraschallbehandlungsdauer das Aspektverhältnis der 1-dimensionalen Strukturen nur gering verändert, die Dispersion der anisotropen Hybridmaterialien perfektioniert und die interpartikulären Kontaktpunkte innerhalb der Mikrostruktur minimiert. Als Ergebnis wurde hierfür die maximal zugängliche spezifische Oberfläche erhalten. Eine Ausweitung dieses Syntheseprotokolls auf Keggin POMs mit unterschiedlicher Ladung, Heteroatomen und Metallkationen konnte auch erfolgreich durchgeführt werden. Katalysetests dieser Hybridzylinder offenbarten dabei Unterschiede in der Aktivität dieser Nanostäbchen in der sauer katalysierten Zersetzung von Isopropanol.
Angliedernd an die ladungsinduzierten Mesostrukturierung wurde ein neues Synthesekonzept zu invers hexagonal geordneten Polymer/ Keggin POM Mesostrukturen erarbeitet. Als organisches Templat wurde Polybutadien-block-poly(2-dimethylaminoethylmethacrylat) (PB-b-PDMAEMA) mit einem hohen Polymerisations-grad des PB-Blockes synthetisiert. Als weitere Schlüsselfaktoren erwiesen sich neben diesem hohen Polymerisationsgrad des PB-Blockes die Wahl des Lösungsmittel und der Keggin POM-Anteil. Um dieses Material auch für Anwendungen wie der Katalyse ansprechend zu machen, muss das polymere Templat am besten vollständig entfernt werden, um eine möglichst hohe Zugänglichkeit der aktiven Zentren zu gewährleisten. Dies wurde sowohl thermisch als auch mit aggressiveren Methoden versucht. Zum einen wurde durch systematische Studien zur thermischen Entfernung des Templates gezeigt, dass die Mesostruktur kollabiert bevor der Kohlenstoff komplett entfernt werden kann. Zum anderen wurde durch aggressivere Methoden, wie Plasmaätzen, erfolgreich der Zugang zu den Mesoporen an Ultradünnschnitten (<50 nm) realisiert. An die thermische Behandlung reihte sich auch die Umwandlung der geordneten Mesophasen in geordnete Carbid/ Kohlenstoff-Nanokomposite an. Letztere sind für Katalyse oder Ladungsspeicherung auch wissenschaftlich interessant. Für die Umwandlung der geordneten oxidischen Mesophasen in Carbid/ Kohlenstoff Nanokomposite wurde nicht versucht das polymere Templat in den Poren zu entfernen, sondern es wurde zum ersten Mal als Kohlenstoffquelle in der Carbidisierungsreaktion verwendet. Folglich lieferten die hergestellten geordneten Mesophasen einen direkten und einfachen Zugang zu porösen Carbid/ Kohlenstoff Nanokompositen und zeigten katalytische Aktivität in der Zersetzung von Ammoniak.
Diese Arbeit ist eine kumulative Dissertation. Die detaillierten Ergebnisse werden in den angehängten Publikationen beschrieben.
Comparisons of N2O and CH4 fluxes as affected by land use systems and climate in small catchments in Korea
- In the course of global and climate change humankind has to face extreme weather events with increased intensity and frequency and it has to deal with feeding an increasing number of people which is accompanied by shortage of resources such as water. Since half of humankind directly depends on freshwater and other ecosystem services provided by mountainous areas, it is essential to study such complex terrains and how natural as well as agricultural systems react to climatic and other anthropogenic changes.
Emissions of greenhouse gases like Nitrous oxide (N2O) and Methane (CH4) are of global concern, too, because they are involved in global warming and therewith: climate change. Major sources of N2O are agriculturally managed soils, and very important sources of CH4 are rice paddies. Thus, it is of great importance to study intensively managed agricultural systems and the effects of the management practices on greenhouse gas emissions.
The major focus of this thesis is to quantify dry crop fields’ and forests’ N2O emissions as well as rice paddies’ N2O and CH4 emissions and to identify climatic as well as management related factors and underlying processes which are driving the N2O fluxes in a complex terrain.
A prolonged early summer drought in 2010 led to significant N2O consumption in soil of three different forest sites. The following above-average monsoon rainfall period indeed turned the N2O consumption into emission but could not turn the N2O balance of a forest on sandy-loam substrate from negative into a positive one, which means that for the first time a negative N2O balance was observed for a forest soil during the growing season. The N2O emissions of those forest sites were clearly driven by soil moisture and temperature and there appeared to be an effect of the substrate on N2O emissions as well, as it is increasingly often observed that sandy-loam soils show significant N2O consumption.
Plastic mulching – a worldwide used method in agriculture to increase crop production by enhancing soil temperature, creating more stable soil moisture conditions and restricting arable weed growth – turned out to have a mitigating effect on N2O emissions. DNDC (Denitrification and Decomposition) modeling results matched best with the measurement results when the maximum daily soil temperature and half of the daily precipitation was assumed to occur as dominating climate conditions underneath the impervious polyethylene (PE) film, suggesting that N2O production underneath the plastic cover was driven by soil moisture and temperature. N2O emissions from a non-fertilized soy bean field, which has Nitrogen fixation as an additional Nitrogen source, were similar to the N2O emissions from a radish field after application of an intermediate amount of N fertilizer of 200 kg ha-1.
Comparing N2O and CH4 emissions from rice paddies under different water management practices showed that intermittent irrigation (II) (no continuous flooding, no water logging)
had the least global warming potential (GWP) which was only 30% of the global warming potential (GWP) of a traditionally irrigated (TI) paddy (continuous flooding and water logging). Another practice of 2.5 months of continuous flooding, followed by midseason drainage and reflooding which created moist but non-water logged conditions (FDFM) lead to 66% of the traditionally irrigated paddies combined CH4 and N2O emissions. These results suggest that a trend towards less flooding has a great potential to mitigate greenhouse gas emissions from a sandy or sandy-loam substrate, respectively. Studying the three paddies’ subsoil conditions revealed that N2O production and consumption processes had mainly taken place between 25 and 50 cm soil depth judging by N2O concentrations and δ15N-N2O values along the soil profiles of all the investigated paddies as well as gene abundances of denitrifying and nitrifying bacteria of the FDFM paddy.
Apart from these important findings on N2O flux dynamics of three different land use systems, it is noticeable that the N2O emissions of the study region are in general very low which is very pleasing and implies that the area deals with global change challenges and associated intensive agriculture in a way that comparatively only small amounts of N2O degas. But this raises the question after the “why?” considering that large amounts of fertilizer are applied on the fields. This thesis does not have a final answer to that question but it discusses whether the sandy substrate may play a major role for the N dynamics of the whole area. There is evidence that NO3- - as the substrate for denitrification - leaches easily due to the soil conditions. To finally figure out why the N2O emissions are that low a more detailed investigation on the fate of NO3- would be desirable.
Charge and excitation-energy transfer in time-dependent density functional theory
- Learning about and understanding the mechanisms and pathways of charge and excitation-energy transfer of natural molecular complexes is a promising approach for the tailored design of new artificial energy-converting materials. Therefore, next to extensive experimental investigations, a theoretical method that is able to reliably describe and predict these phenomena from first principles is of practical relevance. In principle, density functional theory (DFT) and time-dependent density functional theory (TDDFT) appear as natural choices to study the relevant sizable molecules on a first-principles scale at bearable computational cost. However, the application of standard local and semilocal density functional approximations suffers from well-known deficiencies, in particular, as far as the simulation of charge-transfer phenomena is concerned. The present thesis approaches charge and excitation-energy transfer with the objective of improving the predictive power and extending the range of applicability of (TD)DFT.
The deficiencies of standard density functional approximations have been related to self-interaction. Hence, one major aspect of this work is the extension of the self-interaction correction in Kohn-Sham DFT that is based on the generalized optimized effective potential to TDDFT using a real-time propagation approach. The multiplicative Kohn-Sham potential allows for a transparent analysis of the exchange-correlation potential during time evolution. It reveals frequency-dependent field-counteracting behavior and step structures that appear in dynamic charge-transfer situations. The latter are important for the proper description of charge transfer. Self-interaction correction allows to access many cases that are difficult for standard TDDFT ranging from chain-like systems over excitonic excitations in semiconductor nanoclusters to short- and long-range charge-transfer excitations. At the same time, it does not spoil the reasonable accuracy that already (semi)local functionals exhibit for local excitations. Moreover, the TDDFT perspective on self-interaction correction sheds new light also on the ground-state formalism. Complex degrees of freedom in the energy-minimizing transformation of the generalized optimized effective potential approach yield smoother orbital densities that appear more reasonable when inserted into approximate functionals in the self-interaction correction formalism. This work provides new insight into the use of different functional approximations. Last but not least, the influence of spin-symmetry breaking and step structures of the potential on the preference to transfer integer units of the elementary electric charge between largely separated donor and acceptor moieties is illustrated when static external electric fields are applied. This work has been reported in three publications and one submitted manuscript.
In the field of excitation-energy transfer, recent discoveries of quantum coherence effects shed new light on the mechanisms behind energy-transfer rates. The latter are affected by a number of different properties of the isolated molecules, but involve also effects due to the environment of the system. This thesis addresses excitation-energy transfer phenomena from two perspectives. First, I use real-time propagation TDDFT to investigate the intermolecular coupling strength and the coupling mechanism between single fragments of supermolecular setups. These investigations base on standard closed quantum system TDDFT and exploit the coherent oscillation of excitation energy between separated molecules after the initial excitation process. Second, I use open quantum system ideas in the framework of TDDFT to study the influence of the system’s environment on the energy-transfer time scales and pathways in a circular arrangement of molecules using an effective energy-dissipation mechanism. The first part of these results is published. The second part is presented in this thesis and includes work in progress.
Flow and transport processes as affected by tillage management under monsoonal conditions in South Korea
- A sustainable agriculture, which provides enough yields to satisfy the food demand and minimizes the impacts on ecosystem services such as provision of high water quality, is challenging especially in monsoon regions. In this thesis, plastic mulched ridge cultivation (RTpm) under monsoonal conditions and its impact on flow processes and nitrate transport was investigated.
On hillslopes, we monitored surface and subsurface flow processes in four plastic mulched potato fields using a network of tensiometers, FDR sensors, runoff collectors and flow dividers as well as Brilliant Blue FCF tracer experiments. The obtained datasets were used to calibrate the process-based models HYDRUS 2/3D and EROSION 3D in order to quantify drainage water fluxes, surface runoff and erosion rates of RTpm compared to ridge tillage without coverage (RT) and conventional flat tillage (CT). In a flat terrain, N fate under fertilizer rates at 50, 150, 250 and 350 kg NO3− ha−1 was investigated in a plastic mulched radish field using suction lysimeters, tensiometers and a 15N tracer experiment. We used datasets of nitrate concentrations and matric potentials to calibrate a water flow and solute transport model using the numerical code HydroGeoSphere.
RTpm affects soil water dynamics dominantly during dry periods, when ridge soil was drier compared to furrow soil caused by the protective plastic coverage and root water uptake in ridges. Hence, pressure head gradients induced lateral flow from furrows to ridges. Under monsoonal conditions, soil was fully saturated and down slope lateral flow occurred in the coarse textured topsoil. The dye tracer experiments showed that matrix flow dominated in the sandy topsoil. Lateral funnel flow above the tillage pan was the prominent preferential flow path. Unexpectedly, macropore flow in deeper soil horizons was not detected. The field and modeling studies revealed that surface runoff was substantially increased under RTpm compared to RT and CT. However, the field topography primarily controlled surface runoff and erosion rates. The concavity of the field led to flow accumulation and high erosion losses in the center of the field, while a convex shape resulted in less soil erosion.
NO3− leaching was found to be the prominent pathway especially during the early season. Furthermore, the biomass production did not significantly differ between NO3− fertilizer rates of 150 to 350 kg ha−1. Hence, we recommend NO3− fertilizer application of 150 kg ha−1, a better fertilizer placement and split applications. We simulated whether the given recommendations on fertilizer best management practices (FBMPs) decreased NO3− leaching amounts. Compared to RT under conventional fertilization in ridges and furrows, the simulations showed that NO3− leaching can be considerably reduced up to 82% by combining RTpm, fertilizer placement only in ridges and split applications with a total fertilizer NO3− amount of 150 kg ha−1.
Based on these findings, the impact of RTpm on flow and transport processes has to be evaluated differently depending on terrain complexity. In a flat terrain, where surface runoff processes are absent or minimal, RTpm has several advantages. Beside functions such as weed control, and earlier plant emergence due to higher temperatures, plastic mulching decreases drainage water and NO3− leaching. Thus, RTpm enhances nutrient retention below the plastic mulch and reduces NO3− groundwater contamination risk. On slopes, where precipitation contributes substantially to surface runoff, RTpm even increases runoff, soil erosion and surface leaching of agrochemicals into aquatic systems.
This thesis provides several recommendations, aiming to minimize environmental impacts and to decrease costs of fertilizer and herbicide inputs. To reduce surface runoff and soil erosion at sloped fields, we suggest applying perforated plastic mulch and a ridge configuration following contours of the field. Furthermore, we recommend omitting application of herbicides in furrows to allow weed growth, which slows down runoff processes. These suggestions would increase infiltration and subsurface flow processes automatically become more important. However, absent preferential flow to deeper soil layers indicated a low groundwater contamination risk. Since funnel flow above the tillage pan was found to be the most important preferential flow path, we propose the establishment of riparian buffer zones. This would also help to reduce the discharge of sediments and fertilizers via surface runoff into the streams. Finally, FBMPs such as fertilizer placement only in ridges and split applications were found to decrease nitrate leaching considerably. Hence, we suggest applying FBMPs with impermeable plastic mulch in flat terrain, while on hill slopes FBMPs should be applied with perforated plastic mulch. To reduce the leaching and erosion risk after harvest when the plastic mulched ridges are removed, we recommend cultivating cover crops.
Soil erosion and conservation potential of row crop farming in mountainous landscapes of South Korea
- Soils play an essential role for mankind because they provide fundamental ecosystem services required for human life, primarily for the production of food by providing the environment for plant growth. However, soils worldwide became highly threatened by human induced degradation, especially as a consequence of accelerated erosion by water during recent decades. In consideration of climate change and an increasing food demand of a rising population, there is an urgent need to conserve the soil resources by implementing effective erosion control measures for agricultural production. The effective implementation of those measures strongly depends on the specific conditions of particular regions and requires the analysis of the existing farming systems and their capability for erosion control.
Objective of this thesis is the analysis of the major agricultural practices applied for row crop cultivation in mountainous watersheds of South Korea with respect to water erosion and the identification of their conservation potential. Our first two studies analyze the subsurface flow processes, the runoff patterns, and the associated erosion rates of the widely applied plastic covered ridge-furrow system (plastic mulch), and our third study investigates the impact of herbicide applications on erosion associated with conventional and organic farming. To analyze the flow processes induced by the plastic mulch cultivation, we conducted four irrigation experiments on potato fields that represent a smooth surface, uncovered ridges, and plastic covered ridges with and without a developed crop canopy. With an automatic sprinkler, we irrigated small plots with a dye tracer solution of Brilliant Blue and potassium iodide, collected surface runoff, and excavated soil profiles to visualize the subsurface flow patterns, which were subsequently analyzed by image index functions. We found that the ridge-furrow system, especially when ridges are covered with plastic, decreased infiltration and generated high amounts of surface runoff, whereas a developed crop canopy increased infiltration due to interception and stem flow. The analyses of the subsurface flow patterns show that the plastic covered ridge-furrow system induces preferential infiltration in furrows and planting holes due to its topography and the impermeable covers, but that the impact on flow processes in the soils is relatively small compared to the impact on runoff generation. To identify the patterns of overland flow and the erosion rates associated with the plastic mulch system, we installed runoff collectors to monitor runoff and sediment transport of two potato fields with concave and convex topographies, and we applied the EROSION 3D model to compare the plastic covered ridge-furrow system to uncovered ridges and a smooth surface. We found that plastic mulch cultivation considerably increases soil erosion compared to uncovered ridges as a consequence of high amounts of surface runoff. Our results show that the ridge-furrow system concentrated overland flow on the concave field, resulting in severe gully erosion, but prevented flow accumulation and reduced erosion on the convex field, which demonstrates that the effect of this cultivation strategy is primarily controlled by the field topography and its orientation. To analyze the effects of conventional and organic farming on water erosion, we measured multiple vegetation parameters of crops and weeds of conventional and organic farms cultivating bean, potato, radish, and cabbage, and we simulated long-term soil loss rates with the Revised Universal Soil Loss Equation (RUSLE). We found that organic farming reduced erosion for radish, as a result of an increased weed biomass due to the absence of herbicides, but that it increased erosion for potato due to lower crop coverage, presumably as a consequence of crop-weed competition or herbivory associated with the absence of agricultural chemicals. Although we demonstrated that a developed weed cover in the furrows can potentially decrease the erosion risk for row crops, our results show that the average annual erosion rates of both farming systems exceed by far any tolerable soil loss.
In consideration of the generally high soil loss found in our studies, we conclude that the applied farming practices are not capable for effective erosion control and soil conservation in this region. However, based on our findings, we could identify possible modifications of those practices that can help to reduce the risk of erosion in the future. We recommend perforated plastic covers for ridges to reduce runoff generation, and the orientation of the ridge-furrow system along the contours or towards field edges to prevent flow accumulation and gully formation. Additionally, we suggest residue mulching of furrows to protect the soil surface from overland flow, and the cultivation of winter cover crops after harvest to maintain a better soil cover throughout the year.
"The New Chemistry" - Sustainable Catalysis with Alcohols
- Subject of the thesis are new iridium complexes stabilized by anionic P,N- or P,N,P-ligands. These complexes were used in homogeneous catalysis. Furthermore, mechanistic studies were performed to provide an insight into the catalytic cycles. Synthesis protocols for a multitude of different product classes have been developed.
The iridium complex 1, stabilized by a neutral P,N-ligand, reacts under basic conditions with 2-aminopyridines. By elimination of dipyridylamine the new catalyst species 2a was formed, which is more stable than catalyst 1.
Based on this finding eight new anionic P,N-ligands and the resulting iridium complexes were synthesized.
After optimization of the reaction conditions (solvent, base, temperature and catalyst loading) these catalysts were used in BH (borrowing hydrogen)/HA (hydrogen autotransfer) reactions. The selective monoalkylation of anilines with primary alcohols was investigated. In comparative experiments the superiority of the new class of catalysts versus the original catalyst 1 was clearly shown. Under mild reaction conditions (70 °C) the selectivity profile with respect to the monoalkylation has been preserved.
The catalytic protocol was subsequently extended to the alkylation of aromatic diamines. Therefore various diaminobenzenes were used as substrates. Also Dapsone®, an important drug in treatment of leprosy could be used as starting material. We succeeded in both symmetric and unsymmetric monoalkylations of diamines. Due to the selectivity profile of the catalyst regarding aromatic amines, also unprotected amino alcohols could be used as alkylating reagents.
By the use of tridentate P,N,P-ligands, a novel class of more stable catalysts compared to complexes 2a-9a, could be developed. Due to sealing the synthesis reactor with a semipermeable membrane, the retransfer of the “borrowed” hydrogen could be prevented and H2 is released. Dehydrogenation and condensation steps are now possible instead of BH/HA. By reacting secondary alcohols with β-amino alcohols, pyrroles were accessible.
After adapting the synthesis protocol to this new class of products the tolerance of functional groups was tested. Diversely functionalized alcohols were used. Under mild reaction conditions (90 °C) and very low catalyst loadings (down to 0.03 mol% iridium), a large number of novel pyrroles was accessible. Using this protocol 21 differently substituted α,α-pyrroles, 12 bicyclic pyrroles, symmetrically as well as non-symmetrically substituted oligopyrroles and three β-aminopyrroles were synthesized. The catalyst resting state was identified by NMR experiments and X-ray structure analysis to be an iridium trihydride. This trihydride is formed under catalytic conditions, by treatment of the pre-catalyst with alcohols or in hydrogen atmosphere.
In the final part of the work, a catalytic pyridine synthesis was developed. In this so far unknown heterocycle synthesis up to four different substituents could be introduced within a single reaction step. 2,6-, 2,5-, 2,4- and 2,3-substituted pyridines were synthesized selectively by using variously substituted primary or secondary alcohols and γ-amino alcohols. Furthermore, both the synthesis of bicyclic pyridines as well as the synthesis of pyridines that bear chiral substituents is possible.
Functional Triblock Terpolymers for Multicompartment Micelle and Janus Particle Synthesis
- This thesis describes the synthesis of ABC triblock terpolymers with functional moieties via living anionic polymerization, followed by Janus particle (JP) and multicompartment micelle (MCM) synthesis from the as prepared triblock terpolymers.
A synthesis method that can accomplish the tasks of the preparation of spherical as well as non-spherical JPs that are well-defined and in the nanometer size range is based on converting self-assembled triblock terpolymer bulk structures via selective cross-linking of the middle block. Until now such soft JPs were prepared mainly from polystyrene-block-polybutadiene-block-poly(methyl methacrylate) and polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate). However, these polymers do not offer many possibilities of chemical alterations and stimuli-responsive elements.
Therefore, potential new functional monomers for the use in JP synthesis from triblock terpolymer bulk structures were identified and their anionic polymerization examined, p-tert-butoxystyrene (tS) and 4-(dimethylaminomethyl)styrene (DMAMS). Polymers with low polydispersity indices could be prepared from both monomers in tetrahydrofuran (THF) with sec-butyllithium (sec-BuLi) as initiator.
Poly(p-tert-butoxystyrene) (PtS) was hydrolyzed to poly(p-hydroxystyrene) (PHS) which is water-soluble at high pH values, opening the possibility to prepare water-soluble JPs. The pH-responsive behavior of poly(4-(dimethylaminomethyl)styrene) could be confirmed and for the first time an LCST behavior was documented with cloudpoints of 59.3 °C at pH 7 and 28.5 °C at pH 8.
PtS was then used in the preparation of two triblock terpolymers, poly(tert-butoxystyrene)-block-polybutadiene-block-poly(tert-butyl methacrylate) (tSBT) and poly(tert-butoxystyrene)-block-polybutadiene-block-poly(2-(dimethylamino)ethyl methacrylate) (tSBD). tSBT exhibited a lamella-cylinder (lc) bulk morphology with polybutadiene (PB) spheres surrounded by alternating lamellae of PtS and poly(tert-butyl methacrylate) (PtBMA). However, the bulk structure of tSBD consisted of a symmetrical lamella-lamella pattern that is not suitable for JP synthesis.
From tSBT bulk material, three different types of non-spherical JPs could be obtained. Photo-cross-linking of the lamella-cylinder (lc)-morphology by co-casting a radical photo-initiator and UV exposure resulted in the expected Janus cylinders. When the bulk material was first swollen in acetonitrile and cross-linked by cold vulcanization, Janus sheets were obtained. Swelling in acetonitrile/decane emulsion lead to a new type of JPs, Janus ribbons. In both cases a phase transition had occurred; in case of the Janus sheets a thin PB layer had formed between the original PB cylinders, resulting in an undulated-lamella morphology. For the formation of Janus ribbons a connecting PB phase had formed in every second interspace along the major axis of the cylinders. Casting a tSBT film from tert-butanol, a non-solvent for PB, also enabled the synthesis of spherical JPs. This way, the importance and versatile application of swelling agents and cross-linking methods for the preparation of JPs from bulk structures was demonstrated. The obtained Janus cylinders were hydrolyzed to have one PHS and one poly(methacrylic acid) (PMAA) hemicylinder, resulting in water-soluble particles.
Further, solution structures of tSBD and tSBT triblock terpolymers were investigated. In water, tSBD formed core-corona micelles that exhibited pH-responsive and LCST behavior due to the responsive poly(2-(dimethylamino)ethyl methacrylate) corona. Employing the novel method of directed hierarchical self-assembly, “football” MCMs were obtained from tSBD whereas tSBT formed “clover” structures. Cross-linking of the B block in such MCMs and their subsequent dissolution in a solvent for all three blocks can be used to prepare spherical JPs. However, as tSBD MCMs existed in water, no sufficient cross-linking method could be found to cross-link the organic PB phase within the aqueous solution. For tSBT MCMs in ethanol the standard approach of adding a photo-initiator to the MCM solution followed by UV exposure was successfully employed and spherical JPs were obtained. These were again hydrolyzed to acquire water-soluble JPs. Apart from some isolated single Janus spheres, cryogenic transmission electron microscopy mainly revealed the formation of “clover” and “hamburger” oligomers possibly due to the slightly better solubility of PMAA. Here, the applicability of the concept of directed hierarchical self-assembly to create MCMs was demonstrated for two different triblock terpolymers and the corresponding method of solution-based JP synthesis was successfully conducted for tSBT.
Foamy Virus RNase H - Aktivität, Struktur und Funktion
Das für die Replikation des RNA-Genoms von Foamy Viren (FV) notwendige Enzym, die Protease-Reverse Transkriptase (PR-RT), beinhaltet die Protease-, die Polymerase- und RNase H-Domäne. Letztere ist für den Abbau der RNA im entstehenden RNA/DNA Hybrid verantwortlich. Während die FV PR-RT als Monomer vorliegt, besteht die HIV-1 RT aus einem p66/p51-Heterodimer. Erstaunlicherweise ist die isolierte HIV-1 RNase H im Vergleich zur z.B. E. coli oder separaten MoMLV RNase H nicht aktiv. Aus den Sequenzvergleichen verschiedener RNase H-Domänen ergibt sich, dass die Prototyp FV (PFV) RNase H im Gegensatz zur HIV-1 RNase H einen Sekundärstrukturbereich aufweist, bei dem es sich um die sogenannte C-Helix mit einer sich anschließenden basischen Schleife (basic protrusion) handelt. Da zu Beginn der Arbeit keine 3D-Struktur einer retroviralen RNase H mit basic protrusion bekannt war, sollte in dieser Arbeit die Struktur der PFV RNase H und die Funktion der basic protrusion bei der Substratbindung geklärt werden.
Die Tertiärstruktur der PFV RNase H-Domäne konnte mit NMR-Spektroskopie gelöst werden. Somit war es möglich, die basic protrusion einschließlich der C-Helix zu identifizieren. Die isolierte RNase H-Domäne zeigte in fluoreszenzbasierten Tests sowie in qualitativen RNase H-Versuchen mit radioaktiv markiertem Substrat Aktivität. Um die Funktion der C-Helix und der sich anschließenden basischen Schleife bei der Substratbindung zu analysieren, wurden NMR-Titrationsexperimente durchgeführt. Dafür wurde die PFV RNase H-Domäne zunächst durch den Austausch der zwei katalytisch wichtigen Reste Aspartat 599 und Histidin 724 zu Asparagin inaktiviert (RNase H-(D599N-H724N)), um den Abbau des Substrates während der Messungen zu vermeiden. Die Auswertung von [15N, 1H]-HSQC- und [1H, 15N, 1H]-NOESY-HSQC-Spektren erbrachte eine Übereinstimmung der Tertiärstrukturen der RNase H-(D599N-H724N) mit der wt RNase H.
Die NMR-Titrationsexperimente zeigten, dass die C-Helix in der PFV RNase H wie ein Lineal agiert, das die sich anschließende basische Schleife zum Substrat orientiert. Darüber hinaus besitzt die basic protrusion zusätzlich eine Reihe an positiv geladenen Resten, die gut lösungsmittelzugänglich sind und dadurch erste Kontakte mit dem Substrat ermöglichen. Damit bietet die basic protrusion eine Art Plattform für die Substratbindung. Der HIV-1 RNase H fehlt nicht nur die C-Helix, zusätzlich ist die sich anschließende Schleife vermutlich zu kurz, um das Substrat zu binden. Da diese Schleife außerdem nur über einen basischen Rest verfügt, ist wahrscheinlich auch die Gesamtaffinität dieses Bereichs für die Substratbindung zu gering. Strukturvergleiche der PFV RNase H mit der HIV-1 RT zeigen, dass die fehlende basic protrusion der HIV-1 RNase H durch eine Schleife aus der Verbindungs-Subdomäne der p66-Untereinheit kompensiert wird. Dieser Bereich könnte somit ein neuer Angriffspunkt für Inhibitoren in der antiretroviralen Therapie bei HIV 1 sein.
Um zukünftig weitere Strukturanalysen mit der PR-RT bzw. mit einzelnen Domänen durchführen zu können, wurden in einem weiteren Projekt verschiedene N- und C-terminale Deletionsvarianten der PR-RT des Simian Foamy Virus hergestellt. Durch Aktivitätstests mit diesen Deletionsvarianten konnten die Abgrenzungen für die PR-, die Polymerase-, die RNase H-Domäne und die Verbindungs-Subdomäne in der PR-RT identifiziert werden. Dabei zeigte sich, dass die Region H107-N143 C-terminal von der PR wichtig für die Funktion der Polymerase ist. Die Deletion der RNase H-Domäne und Verbindungs-Subdomäne führte zu einer drastischen Abnahme der Substrataffinität, Integrität und Polymerisationsfähigkeit des Enzyms. Trotzdem konnte eine minimale Polymerase-Domäne bestimmt werden (RT(107 454)), die ohne PR- und RNase H-Domäne sowie ohne die Verbindungs-Subdomäne in der Lage ist, zu polymerisieren. Für die Dimerisierung und damit Aktivierung der PR, die durch Bindung von zwei PR-RTs an das sog. PARM-Element (engl. protease activating RNA motif) auf der genomischen RNA geschieht, sind jedoch die RNase H-Domäne und die Verbindungs-Subdomäne unverzichtbar. Dadurch ist die RNase H nicht nur für die reverse Transkription essenziell; in FV stellt sie auch ein Regulationselement für die PR-Aktivierung dar und ist somit indirekt an der Prozessierung von Gag (Strukturproteine) und Pol (virale Enzyme) beteiligt.
Impact of time and spatial averages on the energy balance closure
- Secondary circulations are large and relatively stationary eddies, which are caused by the surface heterogeneity and normally reside away from the ground. They are believed to be the cause of the energy balance closure problem at the earth's surface, because their contribution to the turbulent fluxes is missed by a fixed eddy-covariance tower measurement that has a typical averaging time of 30 minutes. In this thesis, data from the LITFASS-2003 experiment was used to investigate the impact of time and spatial averages on the energy balance closure. This data consisted of many observations over a large heterogeneous landscape that could generate secondary circulations; some of which might be still near the earth's surface.
For the time average analysis, the averaging time was extended to increase the possibility that secondary circulations were picked up by the sensor. Two approaches, which were the modified ogive analysis and the block ensemble average, were applied to analyze the data from ground-based measurements. The modified ogive analysis requiring a steady state condition, could extend the averaging time up to a few hours and suggested that an averaging time of 30 minutes was still overall sufficient for the eddy-covariance measurement over low vegetation. The block ensemble average, on the contrary, did not require a steady state condition, but could extend the averaging time to several days. However, this approach could only improve the energy balance closure for some sites during specific periods, when secondary circulations existed in the vicinity of the sensor. Based on this approach, it was found that the near-surface secondary circulations mainly transported sensible heat, which led to an alternative energy balance correction by the buoyancy flux ratio approach, in which the attribution of the residual depended on the relative contribution of the sensible heat flux to the buoyancy flux. The fraction of the residual attributed to the sensible heat flux by this energy balance correction was larger than in the energy balance correction that preserved the Bowen ratio.
In the spatial average analysis, two energy balance correction approaches, the buoyancy flux ratio and the Bowen ratio approaches, were applied to the area-averaged fluxes (composite fluxes) in order to include contribution from secondary circulations. These composite fluxes were aggregated from multiple ground-based measurements. The energy balance corrected fluxes were validated against the spatial average fluxes, which were measured by an aircraft and a large aperture scintillometer (LAS). In this validation, the backward Lagrangian footprint model was used to estimate the source area of the measurement. It was found that both energy balance correction approaches did improve the agreement between time and spatial averages fluxes. This suggested that the contribution from secondary circulations could be properly accounted by the energy balance correction.
All findings in this thesis, therefore, depict that secondary circulations significantly transport energy in the atmospheric surface layer. The energy balance correction, accomplished by using either the Bowen ratio approach or the buoyancy flux ratio approach, is necessary to estimate the actual vertical transport of energy at the earth's surface.
Structural and electronic properties of transition metal nanoalloys and magnetic compounds
- In transition metal clusters, potentially profitable technological applications and fascinating fundamental questions are closely connected. Bimetallic nanoalloys, e.g., have become increasingly popular as their performance in catalysis is often superior to their pure counterparts. Exemplary for this are gold-platinum (Au-Pt) nanoalloys that have been used as highly potent catalysts in electrocatalysis and in a variety of oxidation reactions. However, the mere existence of Au-Pt nanoalloys is astonishing, as Au and Pt cannot be mixed in bulk over a wide range of compositions. Furthermore, how a combination of Au and Pt in nanoalloys results in their special properties has not yet been determined conclusively.
It has been shown in empirical simulations and first-principles density functional theory (DFT) calculations that Au-Pt nanoalloys preferably arrange in a core-shell mixing pattern with Au forming a shell around a Pt core. This is in contradiction to many experimental studies that report the formation of solid solutions of Au and Pt. In the present work, this seeming discrepancy is addressed by simulating x-ray diffraction patterns that are experimentally used to characterize nanoalloys. It is shown that the interpretation of the diffraction patterns relies on questionable assumptions and therefore does not suffice as a definite characterization tool for Au-Pt nanoalloys.
To shed light on the special catalytic properties of Au-Pt nanoalloys under rather different experimental conditions, a thorough investigation of their electronic and structural properties has been carried out. It is found that features favorable for catalysis in Au-Pt nanoalloys emerge as a consequence of combining two fundamental properties: Pt contributes a high density of states close to the Fermi level, which promotes chemical activity. Au increases the structural flexibility of the Au-Pt system, which might be beneficial for the formation of active and element-specific binding sites as well as regeneration of the catalyst after the reaction.
Although DFT offers an attractive compromise between computational effort and accuracy for a theoretical description of Au-Pt nanoalloys, other transition metal compounds severely challenge existing DFT approximations. Manganese (Mn) doped silicon (Si) clusters represent an ideal model system to study the interaction of a single magnetic impurity with a semiconducting host both experimentally and theoretically. The transition from exohedral (lowly coordinated) to endohedral (highly coordinated) doping that occurs for Si clusters with more than ten atoms, is accompanied by complete quenching of the magnetic moment of Mn. We show that MnSi11+, the smallest endohedral cluster found in experiment, suffers strongly from a well-known general problem of most DFT approximations: the self-interaction error. Finally, a universal correlation between magnetic moment and the coordination of the Mn dopant is established that can be generalized to extended systems and suggests a route to stabilize the magnetic moment of bulk Mn-Si compounds.