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- zentrales Nervensystem (1)
- zweifach schaltbare Blockcopolymere (1)
- zweite Harmonische (1)
- Ärgerregulation (1)
- Überschuldung (1)
- Überschwemmungsflächen (1)
- ß-Lactoglobulin (1)
- öffentlich private Partnerschaften (1)
- öffentliche Verwaltung (1)
- öffentlicher Sektor (1)
Institute
- Institut für Geowissenschaften (26)
- Institut für Chemie (18)
- Institut für Biochemie und Biologie (13)
- Institut für Physik und Astronomie (12)
- Department Linguistik (8)
- Department Sport- und Gesundheitswissenschaften (7)
- Institut für Ernährungswissenschaft (7)
- Institut für Mathematik (7)
- Wirtschaftswissenschaften (7)
- Department Psychologie (6)
This dissertation uses a common grammatical phenomenon, light verb constructions (LVCs) in English and German, to investigate how syntax-semantics mapping defaults influence the relationships between language processing, representation and conceptualization. LVCs are analyzed as a phenomenon of mismatch in the argument structure. The processing implication of this mismatch are experimentally investigated, using ERPs and a dual task. Data from these experiments point to an increase in working memory. Representational questions are investigated using structural priming. Data from this study suggest that while the syntax of LVCs is not different from other structures’, the semantics and mapping are represented differently. This hypothesis is tested with a new categorization paradigm, which reveals that the conceptual structure that LVC evoke differ in interesting, and predictable, ways from non-mismatching structures’.
In the past decades, development cooperation (DC) led by conventional bi- and multilateral donors has been joined by a large number of small, private or public-private donors. This pluralism of actors raises questions as to whether or not these new donors are able to implement projects more or less effectively than their conventional counterparts. In contrast to their predecessors, the new donors have committed themselves to be more pragmatic, innovative and flexible in their development cooperation measures. However, they are also criticized for weakening the function of local civil society and have the reputation of being an intransparent and often controversial alternative to public services. With additional financial resources and their new approach to development, the new donors have been described in the literature as playing a controversial role in transforming development cooperation. This dissertation compares the effectiveness of initiatives by new and conventional donors with regard to the provision of public goods and services to the poor in the water and sanitation sector in India.
India is an emerging country but it is experiencing high poverty rates and poor water supply in predominantly rural areas. It lends itself for analyzing this research theme as it is currently being confronted by a large number of actors and approaches that aim to find solutions for these challenges .
In the theoretical framework of this dissertation, four governance configurations are derived from the interaction of varying actor types with regard to hierarchical and non-hierarchical steering of their interactions. These four governance configurations differ in decision-making responsibilities, accountability and delegation of tasks or direction of information flow. The assumption on actor relationships and steering is supplemented by possible alternative explanations in the empirical investigation, such as resource availability, the inheritance of structures and institutions from previous projects in a project context, gaining acceptance through beneficiaries (local legitimacy) as a door opener, and asymmetries of power in the project context.
Case study evidence from seven projects reveals that the actors' relationship is important for successful project delivery. Additionally, the results show that there is a systematic difference between conventional and new donors. Projects led by conventional donors were consistently more successful, due to an actor relationship that placed the responsibility in the hands of the recipient actors and benefited from the trust and reputation of a long-term cooperation. The trust and reputation of conventional donors always went along with a back-up from federal level and trickled down as reputation also at local level implementation. Furthermore, charismatic leaders, as well as the acquired structures and institutions of predecessor projects, also proved to be a positive influencing factor for successful project implementation.
Despite the mixed results of the seven case studies, central recommendations for action can be derived for the various actors involved in development cooperation. For example, new donors could fulfill a supplementary function with conventional donors by developing innovative project approaches through pilot studies and then implementing them as a supplement to the projects of conventional donors on the ground. In return, conventional donors would have to make room the new donors by integrating their approaches into already programs in order to promote donor harmonization. It is also important to identify and occupy niches for activities and to promote harmonization among donors on state and federal sides.
The empirical results demonstrate the need for a harmonization strategy of different donor types in order to prevent duplication, over-experimentation and the failure of development programs. A transformation to successful and sustainable development cooperation can only be achieved through more coordination processes and national self-responsibility.
In the context of an increasing population of aging people and a shift of medical paradigm towards an individualized medicine in health care, nanostructured lanthanides doped sodium yttrium fluoride (NaYF4) represents an exciting class of upconversion nanomaterials (UCNM) which are suitable to bring forward developments in biomedicine and -biodetection. Despite the fact that among various fluoride based upconversion (UC) phosphors lanthanide doped NaYF4 is one of the most studied upconversion nanomaterial, many open questions are still remaining concerning the interplay of the population routes of sensitizer and activator electronic states involved in different luminescence upconversion photophysics as well as the role of phonon coupling. The collective work aims to explore a detailed understanding of the upconversion mechanism in nanoscaled NaYF4 based materials co-doped with several lanthanides, e.g. Yb3+ and Er3+ as the "standard" type upconversion nanoparticles (UCNP) up to advanced UCNP with Gd3+ and Nd3+. Especially the impact of the crystal lattice structure as well as the resulting lattice phonons on the upconversion luminescence was investigated in detail based on different mixtures of cubic and hexagonal NaYF4 nanoscaled crystals. Three synthesis methods, depending on the attempt of the respective central spectroscopic questions, could be accomplished in the following work. NaYF4 based upconversion nanoparticles doped with several combination of lanthanides (Yb3+, Er3+, Gd3+ and Nd3+) were synthesized successfully using a hydrothermal synthesis method under mild conditions as well as a co-precipitation and a high temperature co-precipitation technique. Structural information were gathered by means of X-ray diffraction (XRD), electron microscopy (TEM), dynamic light scattering (DLS), Raman spectroscopy and inductively coupled plasma atomic emission spectrometry (ICP-OES). The results were discussed in detail with relation to the spectroscopic results. A variable spectroscopic setup was developed for multi parameter upconversion luminescence studies at various temperature 4 K to 328 K. Especially, the study of the thermal behavior of upconversion luminescence as well as time resolved area normalized emission spectra were a prerequisite for the detailed understanding of intramolecular deactivation processes, structural changes upon annealing or Gd3+ concentration, and the role of phonon coupling for the upconversion efficiency. Subsequently it became possible to synthesize UCNP with tailored upconversion luminescence properties. In the end, the potential of UCNP for life science application should be enunciated in context of current needs and improvements of a nanomaterial based optical sensors, whereas the "standard" UCNP design was attuned according to the special conditions in the biological matrix. In terms of a better biocompatibility due to a lower impact on biological tissue and higher penetrability for the excitation light. The first step into this direction was to use Nd3+ ions as a new sensitizer in tridoped NaYF4 based UCNP, whereas the achieved absolute and relative temperature sensitivity is comparable to other types of local temperature sensors in the literature.
Diese Arbeit befasst sich mit der Herstellung und Charakterisierung von thermoresponsiven Filmen auf Goldelektroden durch Fixierung eines bereits synthetisierten thermoresponsiven Polymers. Als Basis für die Entwicklung der responsiven Grenzfläche dienten drei unterschiedliche Copolymere (Polymere I, II und III) aus der Gruppe der thermisch schaltbaren Poly(oligo(ethylenglykol)methacrylate).
Die turbidimetrischen Messungen der Copolymere in Lösungen haben gezeigt, dass der Trübungspunkt vom pH-Wert, der Gegenwart von Salzen sowie von der Ionenstärke der Lösung abhängig ist. Nach der Charakterisierung der Polymere in Lösung wurden Experimente der kovalenten Kopplung der Polymere I bis III an die Oberfläche der Gold-Elektroden durchgeführt. Während bei Polymeren I und II die Ankopplung auf einer Amidverbrückung basierte, wurde bei Polymer III als alternative Methode zur Immobilisierung eine photoinduzierte Anbindung unter gleichzeitiger Vernetzung gewählt. Der Nachweis der erfolgreichen Ankopplung erfolgte bei allen Polymeren elektrochemisch mittels Cyclovoltammetrie und Impedanzspektroskopie in K3/4[Fe(CN)6]-Lösungen. Wie die Ellipsometrie-Messungen zeigten, waren die erhaltenen Polymer-Filme unterschiedlich dick. Die Ankopplung über Amidverbrückung lieferte dünne Filme (10 – 15 nm), während der photovernetzte Film deutlich dicker war (70-80 nm) und die darunter liegende Oberfläche relativ gut isolierte.
Elektrochemische Temperaturexperimente an Polymer-modifizierten Oberflächen in Lösungen in Gegenwart von K3/4[Fe(CN)6] zeigten, dass auch die immobilisierten Polymere I bis III responsives Temperaturverhalten zeigen. Bei Elektroden mit den immobilisierten Polymeren I und II ist der Temperaturverlauf der Parameterwerte diskontinuierlich – ab einem kritischen Punkt (37 °C für Polymer I und 45 °C für Polymer II) wird zunächst langsame Zunahme der Peakströme wird deutlich schneller. Das Temperaturverhalten von Polymer III ist dagegen bis 50 °C kontinuierlich, der Peakstrom sinkt hier durchgehend.
Weiterhin wurde mit den auf Polymeren II und III basierten Elektroden deren Anwendung als responsive Matrix für Bioerkennungsreaktionen untersucht. Es wurde die Ankopplung von kleinen Biorezeptoren, TAG-Peptiden, an Polymer II- und Polymer III-modifizierten Elektroden durchgeführt. Das hydrophile FLAG-TAG-Peptid verändert das Temperaturverhalten des Polymer II-Films unwesentlich, da es die Hydrophilie des Netzwerkes nicht beeinflusst. Weiterhin wurde der Effekt der Ankopplung der ANTI-FLAG-TAG-Antikörper an FLAG-TAG-modifizierte Polymer II-Filme untersucht. Es konnte gezeigt werden, dass die Antikörper spezifisch an FLAG-TAG-modifiziertes Polymer II binden. Es wurde keine unspezifische Anbindung von ANTI-FLAG-TAG an Polymer II beobachtet. Die Temperaturexperimente haben gezeigt, dass die thermische Restrukturierung des Polymer II-FLAG-TAG-Filmes auch nach der Antikörper-Ankopplung noch stattfindet. Der Einfluss der ANTI-FLAG-TAG-Ankopplung ist gering, da der Unterschied in der Hydrophilie zwischen Polymer II und FLAG-TAG bzw. ANTI-FLAG-TAG zu gering ist.
Für die Untersuchungen mit Polymer III-Elektroden wurde neben dem hydrophilen FLAG-TAG-Peptid das deutlich hydrophobere HA-TAG-Peptid ausgewählt. Wie im Falle der Polymer II Elektrode beeinflusst das gekoppelte FLAG-TAG-Peptid das Temperaturverhalten des Polymer III-Netzwerkes nur geringfügig. Die gemessenen Stromwerte sind geringer als bei der Polymer III-Elektrode. Das Temperaturverhalten der FLAG-TAG-Elektrode ähnelt dem der reinen Polymer III-Elektrode – die Stromwerte sinken kontinuierlich bis die Temperatur von ca. 40 °C erreicht ist, bei der ein Plateau beobachtet wird. Offensichtlich verändert FLAG-TAG auch in diesem Fall nicht wesentlich die Hydrophilie des Polymer III-Netzwerkes. Das an Polymer III-Elektroden gekoppelte hydrophobe HA-TAG-Peptid beeinflusst dagegen im starken Maße den Quellzustand des Netzwerkes. Die Ströme für die HA-TAG-Elektroden sind deutlich geringer als die für die FLAG-TAG-Polymer III-Elektroden, was auf geringeren Wassergehalt und dickeren Film zurückzuführen ist. Bereits ab 30 °C erfolgt der Anstieg von Stromwerten, der bei Polymer III- bzw. bei Polymer III-FLAG-TAG-Elektroden nicht beobachtet werden kann. Das gekoppelte hydrophobe HA-TAG-Peptid verdrängt Wasser aus dem Polymer III-Netzwerk, was in der Stauchung des Films bereits bei Raumtemperatur resultiert. Dies führt dazu, dass der Film im Laufe des Temperaturanstieges kaum noch komprimiert. Die Stromwerte steigen in diesem Fall entsprechend des Anstiegs der temperaturabhängigen Diffusion des Redoxpaares. Diese Untersuchungen zeigen, dass das HA-TAG-Peptid als Ankermolekül deutlich besser für eine potentielle Verwendung der Polymer III-Filme für sensorische Zwecke geeignet ist, da es sich deutlich in der Hydrophilie von Polymer III unterscheidet.
In der vorliegenden Arbeit wird die planetare Grenzschicht in Ny-Ålesund, Spitzbergen, sowohl bezüglich kleinskaliger („mikrometeorologischer“) Effekte als auch in ihrer Kopplung mit der Synoptik untersucht. Dazu werden verschiedene Beobachtungsdaten aus der Säule und in Bodennähe zusammengezogen und bewertet. Die so gewonnenen Datensätze werden dann zur Validierung eines nicht-hydrostatischen, regionalen Klimamodells genutzt. Weiterhin werden orographisch bedingte Einflüsse, die Untergrundbeschaffenheit und die lokale Heterogenität der Unterlage untersucht. Hierzu werden meteorologische Größen, wie die Variabilität der Temperatur und insbesondere die jährliche Windverteilung in Bodennähe untersucht und es erfolgt ein Vergleich von in-situ gemessenen turbulenten Flüssen von den Eddy-Kovarianz-Messkomplexen bei Ny-Ålesund und im Bayelva-Tal unter demselben Aspekt. Es zeigt sich, dass der Eddy-Kovarianz-Messkomplex im Bayelva-Tal sehr stark durch eine orographisch bedingte Kanalisierung der Strömung beeinflusst ist und sich nicht für Vergleiche mit regionalen Klimamodellen mit horizontalen Auflösungen von <1km eignet. Die hohe Bodenfeuchte im Bayelva-Tal führt zudem zu einem deutlich kleineren Bowen-Verhältnis, als es für diese Region zu erwarten ist. Der Eddy-Kovarianz-Messkomplex bei Ny-Ålesund erweist sich hingegen als geeigneter für solche Modellvergleiche, aufgrund der typischen, küstennahen Windverteilung und des repräsentativen Footprints. Letzteres wird durch die Bestimmung der Footprint-Klimatologie des Jahres 2013 mit einem aktuellen Footprint-Modell erarbeitet.
Weiterhin wird die Auswirkung von (Anti-) Zyklonen über den Archipel auf die zeitliche Variabilität der lokalen Grenzschichteigenschaften untersucht und bewertet. Dazu wird ein Zyklonen-Detektions-Algorithmus auf ERA-Interim-Reanalysedatensätze angewendet, wodurch die Häufigkeit von nahezu ideal konzentrischen Hoch- und die Tiefdruckgebieten für drei Jahre bestimmt wird. Aus dieser Verteilung werden insgesamt drei interessante Zeiträume zu verschiedenen Jahreszeiten ausgewählt und im Rahmen von Prozessstudien die lokalen bodennahen meteorologischen Messungen, der turbulente Austausch an der Oberfläche und die Grenzschichtdynamik in der Säule untersucht. Die zeitliche Variabilität der dynamischen Grenzschichtstabilität in der Säule wird anhand von zeitlich hoch aufgelösten vertikalen Profilen der Bulk-Richardson-Zahl aus Kompositprofilen aus Fernerkundungsinstrumenten (Radiometer, Wind-LIDAR) sowie Mastdaten (BSRN-Mast) untersucht und die Grenzschichthöhe ermittelt. Aus diesen Analysen ergibt sich eine deutliche Abhängigkeit der thermischen Stabilität beim Durchzug von Fronten, eine damit einhergehende erhebliche Abhängigkeit der Grenzschichtdynamik und der Grenzschichthöhe sowie des turbulenten Austauschs von der zeitlichen Variabilität der Windgeschwindigkeit in der Säule.
Auf Grundlage der Standortanalysen und Prozessstudien erfolgt ein Vergleich der bodennahen Messungen und den Beobachtungen aus der Säule, sowohl von den genannten Fernerkundungsinstrumenten als auch von In-situ-Messungen (Radiosonden) für den Zeitraum einer Radiosondierungskampagne mit dem nicht-hydrostatischen, regionalen Klimamodel WRF (ARW). Auf Grundlage der Fragestellung, inwieweit aktuelle Schemata die Grenzschichtcharakteristika in orographisch stark gegliedertem Gelände in der Arktis reproduzieren können, werden zwei Grenzschichtparametrisierungsschemata mit verschiedenen Ordnungen der Schließung validiert. Hierzu wird die zeitliche Variabilität der Temperatur, der Feuchte und des Windfeldes in der Säule bis 2000m in den Simulationen mit den Beobachtungsdaten vergleichen. Es wird gezeigt, dass durch Modifikation der Initialwertfelder eine sehr gute Übereinstimmung zwischen den Simulationen und den Beobachtungen bereits bei einer horizontalen Auflösung von 1km erreicht werden kann und die Wahl des Grenzschichtschemas nur untergeordneten Einfluss hat. Hieraus werden Ansätze der Weiterentwicklung der Parametrisierungen, aber auch Empfehlungen bezüglich der Initialwertfelder, wie der Landmaske und der Orographie, vorgeschlagen.
Understanding the rates and processes of denudation is key to unraveling the dynamic processes that shape active orogens. This includes decoding the roles of tectonic and climate-driven processes in the long-term evolution of high- mountain landscapes in regions with pronounced tectonic activity and steep climatic and surface-process gradients. Well-constrained denudation rates can be used to address a wide range of geologic problems. In steady-state landscapes, denudation rates are argued to be proportional to tectonic or isostatic uplift rates and provide valuable insight into the tectonic regimes underlying surface denudation. The use of denudation rates based on terrestrial cosmogenic nuclide (TCN) such as 10Beryllium has become a widely-used method to quantify catchment-mean denudation rates. Because such measurements are averaged over timescales of 102 to 105 years, they are not as susceptible to stochastic changes as shorter-term denudation rate estimates (e.g., from suspended sediment measurements) and are therefore considered more reliable for a comparison to long-term processes that operate on geologic timescales. However, the impact of various climatic, biotic, and surface processes on 10Be concentrations and the resultant denudation rates remains unclear and is subject to ongoing discussion. In this thesis, I explore the interaction of climate, the biosphere, topography, and geology in forcing and modulating denudation rates on catchment to orogen scales.
There are many processes in highly dynamic active orogens that may effect 10Be concentrations in modern river sands and therefore impact 10Be-derived denudation rates. The calculation of denudation rates from 10Be concentrations, however, requires a suite of simplifying assumptions that may not be valid or applicable in many orogens. I investigate how these processes affect 10Be concentrations in the Arun Valley of Eastern Nepal using 34 new 10Be measurements from the main stem Arun River and its tributaries. The Arun Valley is characterized by steep gradients in climate and topography, with elevations ranging from <100 m asl in the foreland basin to >8,000 asl in the high sectors to the north. This is coupled with a five-fold increase in mean annual rainfall across strike of the orogen. Denudation rates from tributary samples increase toward the core of the orogen, from <0.2 to >5 mm/yr from the Lesser to Higher Himalaya. Very high denudation rates (>2 mm/yr), however, are likely the result of 10Be TCN dilution by surface and climatic processes, such as large landsliding and glaciation, and thus may not be representative of long-term denudation rates. Mainstem Arun denudation rates increase downstream from ~0.2 mm/yr at the border with Tibet to 0.91 mm/yr at its outlet into the Sapt Kosi. However, the downstream 10Be concentrations may not be representative of the entire upstream catchment. Instead, I document evidence for downstream fining of grains from the Tibetan Plateau, resulting in an order-of-magnitude apparent decrease in the measured 10Be concentration.
In the Arun Valley and across the Himalaya, topography, climate, and vegetation are strongly interrelated. The observed increase in denudation rates at the transition from the Lesser to Higher Himalaya corresponds to abrupt increases in elevation, hillslope gradient, and mean annual rainfall. Thus, across strike (N-S), it is difficult to decipher the potential impacts of climate and vegetation cover on denudation rates. To further evaluate these relationships I instead took advantage of an along-strike west-to-east increase of mean annual rainfall and vegetation density in the Himalaya. An analysis of 136 published 10Be denudation rates from along strike of the revealed that median denudation rates do not vary considerably along strike of the Himalaya, ~1500 km E-W. However, the range of denudation rates generally decreases from west to east, with more variable denudation rates in the northwestern regions of the orogen than in the eastern regions. This denudation rate variability decreases as vegetation density increases (R=- 0.90), and increases proportionately to the annual seasonality of vegetation (R=0.99). Moreover, rainfall and vegetation modulate the relationship between topographic steepness and denudation rates such that in the wet, densely vegetated regions of the Himalaya, topography responds more linearly to changes in denudation rates than in dry, sparsely vegetated regions, where the response of topographic steepness to denudation rates is highly nonlinear. Understanding the relationships between denudation rates, topography, and climate is also critical for interpreting sedimentary archives. However, there is a lack of understanding of how terrestrial organic matter is transported out of orogens and into sedimentary archives. Plant wax lipid biomarkers derived from terrestrial and marine sedimentary records are commonly used as paleo- hydrologic proxy to help elucidate these problems. I address the issue of how to interpret the biomarker record by using the plant wax isotopic composition of modern suspended and riverbank organic matter to identify and quantify organic matter source regions in the Arun Valley. Topographic and geomorphic analysis, provided by the 10Be catchment-mean denudation rates, reveals that a combination of topographic steepness (as a proxy for denudation) and vegetation density is required to capture organic matter sourcing in the Arun River.
My studies highlight the importance of a rigorous and careful interpretation of denudation rates in tectonically active orogens that are furthermore characterized by strong climatic and biotic gradients. Unambiguous information about these issues is critical for correctly decoding and interpreting the possible tectonic and climatic forces that drive erosion and denudation, and the manifestation of the erosion products in sedimentary archives.
In this thesis, the two prototype catalysts Fe(CO)₅ and Cr(CO)₆ are investigated with time-resolved photoelectron spectroscopy at a high harmonic setup. In both of these metal carbonyls, a UV photon can induce the dissociation of one or more ligands of the complex. The mechanism of the dissociation has been debated over the last decades. The electronic dynamics of the first dissociation occur on the femtosecond timescale.
For the experiment, an existing high harmonic setup was moved to a new location, was extended, and characterized. The modified setup can induce dynamics in gas phase samples with photon energies of 1.55eV, 3.10eV, and 4.65eV. The valence electronic structure of the samples can be probed with photon energies between 20eV and 40eV. The temporal resolution is 111fs to 262fs, depending on the combination of the two photon energies.
The electronically excited intermediates of the two complexes, as well as of the reaction product Fe(CO)₄, could be observed with photoelectron spectroscopy in the gas phase for the first time. However, photoelectron spectroscopy gives access only to the final ionic states. Corresponding calculations to simulate these spectra are still in development. The peak energies and their evolution in time with respect to the initiation pump pulse have been determined, these peaks have been assigned based on literature data. The spectra of the two complexes show clear differences. The dynamics have been interpreted with the assumption that the motion of peaks in the spectra relates to the movement of the wave packet in the multidimensional energy landscape. The results largely confirm existing models for the reaction pathways. In both metal carbonyls, this pathway involves a direct excitation of the wave packet to a metal-to-ligand charge transfer state and the subsequent crossing to a dissociative ligand field state. The coupling of the electronic dynamics to the nuclear dynamics could explain the slower dissociation in Fe(CO)₅ as compared to Cr(CO)₆.
In complement to the well-established zwitterionic monomers 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (“SPE”) and 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (“SPP”), the closely related sulfobetaine monomers were synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar mass were characterized with respect to their solubility in water, deuterated water, and aqueous salt solutions. These poly(sulfobetaine)s show thermoresponsive behavior in water, exhibiting upper critical solution temperatures (UCST). Phase transition temperatures depend notably on the molar mass and polymer concentration, and are much higher in D2O than in H2O. Also, the phase transition temperatures are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed structure of the zwitterionic side chain, on the other hand. For the polymers with the same zwitterionic side chain, it is found that methacrylamide-based poly(sulfobetaine)s exhibit higher UCST-type transition temperatures than their methacrylate analogs. The extension of the distance between polymerizable unit and zwitterionic groups from 2 to 3 methylene units decreases the UCST-type transition temperatures. Poly(sulfobetaine)s derived from aliphatic esters show higher UCST-type transition temperatures than their analogs featuring cyclic ammonium cations. The UCST-type transition temperatures increase markedly with spacer length separating the cationic and anionic moieties from 3 to 4 methylene units. Thus, apparently small variations of their chemical structure strongly affect the phase behavior of the polyzwitterions in specific aqueous environments.
Water-soluble block copolymers were prepared from the zwitterionic monomers and the non-ionic monomer N-isopropylmethacrylamide (“NIPMAM”) by the RAFT polymerization. Such block copolymers with two hydrophilic blocks exhibit twofold thermoresponsive behavior in water. The poly(sulfobetaine) block shows an UCST, whereas the poly(NIPMAM) block exhibits a lower critical solution temperature (LCST). This constellation induces a structure inversion of the solvophobic aggregate, called “schizophrenic micelle”. Depending on the relative positions of the two different phase transitions, the block copolymer passes through a molecularly dissolved or an insoluble intermediate regime, which can be modulated by the polymer concentration or by the addition of salt. Whereas, at low temperature, the poly(sulfobetaine) block forms polar aggregates that are kept in solution by the poly(NIPMAM) block, at high temperature, the poly(NIPMAM) block forms hydrophobic aggregates that are kept in solution by the poly(sulfobetaine) block. Thus, aggregates can be prepared in water, which switch reversibly their “inside” to the “outside”, and vice versa.
It is commonly recognized that soil moisture exhibits spatial heterogeneities occurring in a wide range of scales. These heterogeneities are caused by different factors ranging from soil structure at the plot scale to land use at the landscape scale. There is an urgent need for effi-cient approaches to deal with soil moisture heterogeneity at large scales, where manage-ment decisions are usually made. The aim of this dissertation was to test innovative ap-proaches for making efficient use of standard soil hydrological data in order to assess seep-age rates and main controls on observed hydrological behavior, including the role of soil het-erogeneities.
As a first step, the applicability of a simplified Buckingham-Darcy method to estimate deep seepage fluxes from point information of soil moisture dynamics was assessed. This was done in a numerical experiment considering a broad range of soil textures and textural het-erogeneities. The method performed well for most soil texture classes. However, in pure sand where seepage fluxes were dominated by heterogeneous flow fields it turned out to be not applicable, because it simply neglects the effect of water flow heterogeneity. In this study a need for new efficient approaches to handle heterogeneities in one-dimensional water flux models was identified.
As a further step, an approach to turn the problem of soil moisture heterogeneity into a solu-tion was presented: Principal component analysis was applied to make use of the variability among soil moisture time series for analyzing apparently complex soil hydrological systems. It can be used for identifying the main controls on the hydrological behavior, quantifying their relevance, and describing their particular effects by functional averaged time series. The ap-proach was firstly tested with soil moisture time series simulated for different texture classes in homogeneous and heterogeneous model domains. Afterwards, it was applied to 57 mois-ture time series measured in a multifactorial long term field experiment in Northeast Germa-ny.
The dimensionality of both data sets was rather low, because more than 85 % of the total moisture variance could already be explained by the hydrological input signal and by signal transformation with soil depth. The perspective of signal transformation, i.e. analyzing how hydrological input signals (e.g., rainfall, snow melt) propagate through the vadose zone, turned out to be a valuable supplement to the common mass flux considerations. Neither different textures nor spatial heterogeneities affected the general kind of signal transfor-mation showing that complex spatial structures do not necessarily evoke a complex hydro-logical behavior. In case of the field measured data another 3.6% of the total variance was unambiguously explained by different cropping systems. Additionally, it was shown that dif-ferent soil tillage practices did not affect the soil moisture dynamics at all.
The presented approach does not require a priori assumptions about the nature of physical processes, and it is not restricted to specific scales. Thus, it opens various possibilities to in-corporate the key information from monitoring data sets into the modeling exercise and thereby reduce model uncertainties.
This doctoral thesis seeks to elaborate how Wittgenstein’s very sparse writings on ethics and ethical thought, together with his later work on the more general problem of normativity and his approach to philosophical problems as a whole, can be applied to contemporary meta-ethical debates about the nature of moral thought and language and the sources of moral obligation. I begin with a discussion of Wittgenstein’s early “Lecture on Ethics”, distinguishing the thesis of a strict fact/value dichotomy that Wittgenstein defends there from the related thesis that all ethical discourse is essentially and intentionally nonsensical, an attempt to go beyond the limits of sense. The first chapter discusses and defends Wittgenstein’s argument that moral valuation always goes beyond any ascertaining of fact; the second chapter seeks to draw out the valuable insights from Wittgenstein’s (early) insistence that value discourse is nonsensical while also arguing that this thesis is ultimately untenable and also incompatible with later Wittgensteinian understanding of language. On the basis of this discussion I then take up the writings of the American philosopher Cora Diamond, who has worked out an ethical approach in a very closely Wittgensteinian spirit, and show how this approach shares many of the valuable insights of the moral expressivism and constructivism of contemporary authors such as Blackburn and Korsgaard while suggesting a way to avoid some of the problems and limitations of their approaches. Subsequently I turn to a criticism of the attempts by Lovibond and McDowell to enlist Wittgenstein in the support for a non-naturalist moral realism. A concluding chapter treats the ways that a broadly Wittgensteinian conception expands the subject of metaethics itself by questioning the primacy of discursive argument in moral thought and of moral propositions as the basic units of moral belief.