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The introduction of columnar in-memory databases, along with hardware evolution, has made the execution of transactional and analytical enterprise application workloads on a single system both feasible and viable. Yet, we argue that executing analytical aggregate queries directly on the transactional data can decrease the overall system performance. Despite the aggregation capabilities of columnar in-memory databases, the direct access to records of a materialized aggregate is always more efficient than aggregating on the fly. The traditional approach to materialized aggregates, however, introduces significant overhead in terms of materialized view selection, maintenance, and exploitation. When this overhead is handled by the application, it increases the application complexity, and can slow down the transactional throughput of inserts, updates, and deletes.
In this thesis, we motivate, propose, and evaluate the aggregate cache, a materialized aggregate engine in the main-delta architecture of a columnar in-memory database that provides efficient means to handle costly aggregate queries of enterprise applications. For our design, we leverage the specifics of the main-delta architecture that separates a table into a main and delta partition. The central concept is to only cache the partial aggregate query result as defined on the main partition of a table, because the main partition is relatively stable as records are only inserted into the delta partition. We contribute by proposing incremental aggregate maintenance and query compensation techniques for mixed workloads of enterprise applications. In addition, we introduce aggregate profit metrics that increase the likelihood of persisting the most profitable aggregates in the aggregate cache.
Query compensation and maintenance of materialized aggregates based on joins of multiple tables is expensive due to the partitioned tables in the main-delta architecture. Our analysis of enterprise applications has revealed several data schema and workload patterns. This includes the observation that transactional data is persisted in header and item tables, whereas in many cases, the insertion of related header and item records is executed in a single database transaction. We contribute by proposing an approach to transport these application object semantics to the database system and optimize the query processing using the aggregate cache by applying partition pruning and predicate pushdown techniques.
For the experimental evaluation, we propose the FICO benchmark that is based on data from a productive ERP system with extracted mixed workloads. Our evaluation reveals that the aggregate cache can accelerate the execution of aggregate queries up to a factor of 60 whereas the speedup highly depends on the number of aggregated records in the main and delta partitions. In mixed workloads, the proposed aggregate maintenance and query compensation techniques perform up to an order of magnitude better than traditional materialized aggregate maintenance approaches. The introduced aggregate profit metrics outperform existing costbased metrics by up to 20%. Lastly, the join pruning and predicate pushdown techniques can accelerate query execution in the aggregate cache in the presence of multiple partitioned tables by up to an order of magnitude.
In the first part of my work I have investigated the ageing properties of the first passage time distributions in a one-dimensional subdiffusive continuous time random walk with power law distributed waiting times of the form $\psi(\tau) \sim \tau^{-1-\alpha}$ with $0<\alpha<1$ and $1<\alpha<2$. The age or ageing time $t_a$ is the time span from the start of the stochastic process to the start of the observation of this process (at $t=0$). I have calculated the results for a single target and two targets, also including the biased case, where the walker is driven towards the boundary by a constant force. I have furthermore refined the previously derived results for the non-ageing case and investigated the changes that occur when the walk is performed in a discrete quenched energy landscape, where the waiting times are fixed for every site. The results include the exact Laplace space densities and infinite (converging) series as exact results in the time space. The main results are the dominating long time power law behavior regimes, which depend on the ageing time. For the case of unbiased subdiffusion ($\alpha < 1$) in the presence of one target, I find three different dominant terms for ranges of $t$ separated by $t_a$ and another crossover time $t^{\star}$, which depends on $t_a$ as well as on the anomalous exponent $\alpha$ and the anomalous diffusion coefficient $K_{\alpha}$. In all three regimes ($t \ll t_a$, $t_a \ll t \ll t^{\star}$, $t \gg t^{\star}$) one finds power law decay with exponents depending on $\alpha$. The middle regime only exists for $t_a \ll t^{\star}$. The dominant terms in the first two regimes (ageing regimes) come from the probability distribution of the forward waiting time, the time one has to wait for the stochastic process to make the first step during the observation. When the observation time is larger than the second crossover time $t^{\star}$, the first passage time density does not show ageing and the non-ageing first passage time dominates. The power law exponents in the respective regimes are $-\alpha$ for strong ageing, $-1-\alpha$ in the intermediate regime, and $-1-\alpha/2$ in the final non-ageing regime. A similar split into three regimes can be found for $1<\alpha<2$, only with a different second crossover time $t^*$. In this regime the diffusion is normal but also age-dependent. For the diffusion in quenched energy landscapes one cannot detect ageing. The first passage time density shows a quenched power law $^\sim t^{-(1+2\alpha)/(1+\alpha)}$. For diffusion between two target sites and the biased diffusion towards a target only two scaling regimes emerge, separated by the ageing time. In the ageing case $t \ll t_a$ the forward waiting time is again dominant with power law exponent $-\alpha$, while the non-ageing power law $-1-\alpha$ is found for all times $t \gg t_a$. An intermediate regime does not exist. The bias and the confinement have similar effects on the first passage time density. For quenched diffusion, the biased case is interesting, as the bias reduces correlations due to revisiting of the same waiting time. As a result, CTRW like behavior is observed, including ageing. Extensive computer simulations support my findings.
The second part of my research was done on the subject of ageing Scher-Montroll transport, which is in parts closely related to the first passage densities. It explains the electrical current in an amorphous material. I have investigated the effect of the width of a given initial distribution of charge carriers on the transport coefficients as well as the ageing effect on the emerging power law regimes and a constant initial regime. While a spread out initial distribution has only little impact on the Scher-Montroll current, ageing alters the behavior drastically. Instead of the two classical power laws one finds four current regimes, up to three of which can appear in a single experiment. The dominant power laws differ for $t \ll t_a, t_c$, $t_a \ll t \ll t_c$, $t_c \ll t \ll t_a$, and $t \gg t_a,t_c$. Here, $t_c$ is the crossover time of the non-aged Scher-Montroll current. For strongly aged systems one can observe a constant current in the first regime while the others are dominated by decaying power laws with exponents $\alpha -1$, $-\alpha$, and $-1-\alpha$. The ageing regimes are the 1st and 3rd one, while the classical regimes are the 2nd and the 4th. I have verified the theory using numerical integration of the exact integrals and applied the new results to experimental data.
In the third part I considered a single file of subdiffusing particles in an energy landscape. Every occupied site of the landscape acts as a boundary, from which a particle is immediately reflected to its previous site, if it tries to jump there. I have analysed the effects single-file diffusion a quenched landscape compared to an annealed landscape and I have related these results to the number of steps and related quantities. The diffusion changes from ultraslow logarithmic diffusion in the annealed or CTRW case to subdiffusion with an anomalous exponent $\alpha/(1+\alpha)$ in the quenched landscape. The behavior is caused by the forward waiting time, which changes drastically from the quenched to the annealed case. Single-file effects in the quenched landscape are even more complicated to consider in the ensemble average, since the diffusion in individual landscapes shows extremely diverse behavior. Extensive simulations support my theoretical arguments, which consider mainly the long time evolution of the mean square displacement of a bulk particle.
A majority of studies documented a reduced ankle muscle activity, particularly of the peroneus longus muscle (PL), in patients with functional ankle instability (FI). It is considered valid that foot orthoses as well as sensorimotor training have a positive effect on ankle muscle activity in healthy individuals and those with lower limb overuse injuries or flat arched feet (reduced reaction time by sensorimotor exercises; increased ankle muscle amplitude by orthoses use). However, the acute- and long-term influence of foot orthoses on ankle muscle activity in individuals with FI is unknown.
AIMS: The present thesis addressed (1a) acute- and (1b) long-term effects of foot orthoses compared to sensorimotor training on ankle muscle activity in patients with FI. (2) Further, it was investigated if the orthosis intervention group demonstrate higher ankle muscle activity by additional short-term use of a measurement in-shoe orthosis (compared to short-term use of “shoe only”) after intervention. (3) As prerequisite, it was evaluated if ankle muscle activity can be tested reliably and (4) if this differs between healthy individuals and those with FI.
METHODS: Three intervention groups (orthosis group [OG], sensorimotor training group [SMTG], control group [CG]), consisting of both, healthy individuals and those with FI, underwent one longitudinal investigation (randomised controlled trial). Throughout 6 weeks of intervention, OG wore an in-shoe orthosis with a specific “PL stimulation module”, whereas SMTG conducted home-based exercises. CG served to measure test-retest reliability of ankle muscle activity (PL, M. tibialis anterior [TA] and M. gastrocnemius medialis [GM]). Pre- and post-intervention, ankle muscle activity (EMG amplitude) was recorded during “normal” unperturbed (NW) and perturbed walking (PW) on a split-belt treadmill (stimulus 200 ms post initial heel contact [IC]) as well as during side cutting (SC), each while wearing “shoes only” and additional measurement in-shoe orthoses (randomized order). Normalized RMS values (100% MVC, mean±SD) were calculated pre- (100-50 ms) and post (200-400 ms) - IC.
RESULTS: (3) Test-retest reliability showed a high range of values in healthy individuals and those with FI. (4) Compared to healthy individuals, patients with FI demonstrated lower PL pre-activity during SC, however higher PL pre-activity for NW and PW. (1a) Acute orthoses use did not influence ankle muscle activity. (1b) For most conditions, sensorimotor training was more effective in individuals with FI than long-term orthotic intervention (increased: PL and GM pre-activity and TA reflex-activity for NW, PL pre-activity and TA, PL and GM reflex-activity for SC, PL reflex-activity for PW). However, prolonged orthoses use was more beneficial in terms of an increase in GM pre-activity during SC. For some conditions, long-term orthoses intervention was as effective as sensorimotor training for individuals with FI (increased: PL pre-activity for PW, TA pre-activity for SC, PL and GM reflex-activity for NW). Prolonged orthoses use was also advantageous in healthy individuals (increased: PL and GM pre-activity for NW and PW, PL pre-activity for SC, TA and PL reflex-activity for NW, PL and GM reflex-activity for PW). (2) The orthosis intervention group did not present higher ankle muscle activity by the additional short-term use of a measurement in-shoe orthosis at re-test after intervention.
CONCLUSION: High variations of reproducibility reflect physiological variability in muscle activity during gait and therefore deemed acceptable. The main findings confirm the presence of sensorimotor long-term effects of specific foot orthoses in healthy individuals (primary preventive effect) and those with FI (therapeutic effect). Neuromuscular compensatory feedback- as well as anticipatory feedforward adaptation mechanism to prolonged orthoses use, specifically of the PL muscle, underpins the key role of PL in providing essential dynamic ankle joint stability. Due to its advantages over sensorimotor training (positive subjective feedback in terms of comfort, time-and-cost-effectiveness), long-term foot orthoses use can be recommended as an applicable therapy alternative in the treatment of FI. Long-term effect of foot orthoses in a population with FI must be validated in a larger sample size with longer follow-up periods to substantiate the generalizability of the existing outcomes.
The impact of soil microbiota on plant species performance and diversity in semi-natural grasslands
(2016)
Over the past decades, rapid and constant advances have motivated GNSS technology to approach the ability to monitor transient ground motions with mm to cm accuracy in real-time. As a result, the potential of using real-time GNSS for natural hazards prediction and early warning has been exploited intensively in recent years, e.g., landslides and volcanic eruptions monitoring. Of particular note, compared with traditional seismic instruments, GNSS does not saturate or tilt in terms of co-seismic displacement retrieving, which makes it especially valuable for earthquake and earthquake induced tsunami early warning. In this thesis, we focus on the application of real-time GNSS to fast seismic source inversion and tsunami early warning.
Firstly, we present a new approach to get precise co-seismic displacements using cost effective single-frequency receivers. As is well known, with regard to high precision positioning, the main obstacle for single-frequency GPS receiver is ionospheric delay. Considering that over a few minutes, the change of ionospheric delay is almost linear, we constructed a linear model for each satellite to predict ionospheric delay. The effectiveness of this method has been validated by an out-door experiment and 2011 Tohoku event, which confirms feasibility of using dense GPS networks for geo-hazard early warning at an affordable cost.
Secondly, we extended temporal point positioning from GPS-only to GPS/GLONASS and assessed the potential benefits of multi-GNSS for co-seismic displacement determination. Out-door experiments reveal that when observations are conducted in an adversary environment, adding a couple of GLONASS satellites could provide more reliable results. The case study of 2015 Illapel Mw 8.3 earthquake shows that the biases between co-seismic displacements derived from GPS-only and GPS/GLONASS vary from station to station, and could be up to 2 cm in horizontal direction and almost 3 cm in vertical direction. Furthermore, slips inverted from GPS/GLONASS co-seismic displacements using a layered crust structure on a curved plane are shallower and larger for the Illapel event.
Thirdly, we tested different inversion tools and discussed the uncertainties of using real-time GNSS for tsunami early warning. To be exact, centroid moment tensor inversion, uniform slip inversion using a single Okada fault and distributed slip inversion in layered crust on a curved plane were conducted using co-seismic displacements recorded during 2014 Pisagua earthquake. While the inversion results give similar magnitude and the rupture center, there are significant differences in depth, strike, dip and rake angles, which lead to different tsunami propagation scenarios. Even though, resulting tsunami forecasting along the Chilean coast is close to each other for all three models.
Finally, based on the fact that the positioning performance of BDS is now equivalent to GPS in Asia-Pacific area and Manila subduction zone has been identified as a zone of potential tsunami hazard, we suggested a conceptual BDS/GPS network for tsunami early warning in South China Sea. Numerical simulations with two earthquakes (Mw 8.0 and Mw 7.5) and induced tsunamis demonstrate the viability of this network. In addition, the advantage of BDS/GPS over a single GNSS system by source inversion grows with decreasing earthquake magnitudes.
The horse is a fascinating animal symbolizing power, beauty, strength and grace. Among all the animal species domesticated the horse had the largest impact on the course of human history due to its importance for warfare and transportation. Studying the process of horse domestication contributes to the knowledge about the history of horses and even of our own species.
Research based on molecular methods has increasingly focused on the genetic basis of horse domestication. Mitochondrial DNA (mtDNA) analyses of modern and ancient horses detected immense maternal diversity, probably due to many mares that contributed to the domestic population. However, mtDNA does not provide an informative phylogeographic structure. In contrast, Y chromosome analyses displayed almost complete uniformity in modern stallions but relatively high diversity in a few ancient horses. Further molecular markers that seem to be well suited to infer the domestication history of horses or genetic and phenotypic changes during this process are loci associated with phenotypic traits.
This doctoral thesis consists of three different parts for which I analyzed various single nucleotide polymorphisms (SNPs) associated with coat color, locomotion or Y chromosomal variation of horses. These SNPs were genotyped in 350 ancient horses from the Chalcolithic (5,000 BC) to the Middle Ages (11th century). The distribution of the samples ranges from China to the Iberian Peninsula and Iceland. By applying multiplexed next-generation sequencing (NGS) I sequenced short amplicons covering the relevant positions: i) eight coat-color-associated mutations in six genes to deduce the coat color phenotype; ii) the so-called ’Gait-keeper’ SNP in the DMRT3 gene to screen for the ability to amble; iii) 16 SNPs previously detected in ancient horses to infer the corresponding haplotype. Based on these data I investigated the occurrence and frequencies of alleles underlying the respective phenotypes as well as Y chromosome haplotypes at different times and regions. Also, selection coefficients for several Y chromosome lineages or phenotypes were estimated.
Concerning coat color differences in ancient horses my work constitutes the most comprehensive study to date. I detected an increase of chestnut horses in the Middle Ages as well as differential selection for spotted and solid phenotypes over time which reflects changing human preferences.
With regard to ambling horses, the corresponding allele was present in medieval English and Icelandic horses. Based on these results I argue that Norse settlers, who frequently invaded parts of Britain, brought ambling individuals to Iceland from the British Isles which can be regarded the origin of this trait. Moreover, these settlers appear to have selected for ambling in Icelandic horses.
Relating to the third trait, the paternal diversity, these findings represent the largest ancient dataset of Y chromosome variation in non-humans. I proved the existence of several Y chromosome haplotypes in early domestic horses. The decline of Y chromosome variation coincides with the movement of nomadic peoples from the Eurasian steppes and later with different breeding practices in the Roman period.
In conclusion, positive selection was estimated for several phenotypes/lineages
in different regions or times which indicates that these were preferred by humans. Furthermore, I could successfully infer the distribution and dispersal of horses in association with human movements and actions. Thereby, a better understanding of the influence of people on the changing appearance and genetic diversity of domestic horses could be gained. My results also emphasize the close relationship of ancient genetics and archeology or history and that only in combination well-founded conclusions can be reached.
Geospatial data has become a natural part of a growing number of information systems and services in the economy, society, and people's personal lives. In particular, virtual 3D city and landscape models constitute valuable information sources within a wide variety of applications such as urban planning, navigation, tourist information, and disaster management. Today, these models are often visualized in detail to provide realistic imagery. However, a photorealistic rendering does not automatically lead to high image quality, with respect to an effective information transfer, which requires important or prioritized information to be interactively highlighted in a context-dependent manner.
Approaches in non-photorealistic renderings particularly consider a user's task and camera perspective when attempting optimal expression, recognition, and communication of important or prioritized information. However, the design and implementation of non-photorealistic rendering techniques for 3D geospatial data pose a number of challenges, especially when inherently complex geometry, appearance, and thematic data must be processed interactively. Hence, a promising technical foundation is established by the programmable and parallel computing architecture of graphics processing units.
This thesis proposes non-photorealistic rendering techniques that enable both the computation and selection of the abstraction level of 3D geospatial model contents according to user interaction and dynamically changing thematic information. To achieve this goal, the techniques integrate with hardware-accelerated rendering pipelines using shader technologies of graphics processing units for real-time image synthesis. The techniques employ principles of artistic rendering, cartographic generalization, and 3D semiotics—unlike photorealistic rendering—to synthesize illustrative renditions of geospatial feature type entities such as water surfaces, buildings, and infrastructure networks. In addition, this thesis contributes a generic system that enables to integrate different graphic styles—photorealistic and non-photorealistic—and provide their seamless transition according to user tasks, camera view, and image resolution.
Evaluations of the proposed techniques have demonstrated their significance to the field of geospatial information visualization including topics such as spatial perception, cognition, and mapping. In addition, the applications in illustrative and focus+context visualization have reflected their potential impact on optimizing the information transfer regarding factors such as cognitive load, integration of non-realistic information, visualization of uncertainty, and visualization on small displays.
The ever-increasing fat content in Western diet, combined with decreased levels of physical activity, greatly enhance the incidence of metabolic-related diseases. Cancer cachexia (CC) and Metabolic syndrome (MetS) are both multifactorial highly complex metabolism related syndromes, whose etiology is not fully understood, as the mechanisms underlying their development are not completely unveiled. Nevertheless, despite being considered “opposite sides”, MetS and CC share several common issues such as insulin resistance and low-grade inflammation. In these scenarios, tissue macrophages act as key players, due to their capacity to produce and release inflammatory mediators. One of the main features of MetS is hyperinsulinemia, which is generally associated with an attempt of the β-cell to compensate for diminished insulin sensitivity (insulin resistance). There is growing evidence that hyperinsulinemia per se may contribute to the development of insulin resistance, through the establishment of low grade inflammation in insulin responsive tissues, especially in the liver (as insulin is secreted by the pancreas into the portal circulation). The hypothesis of the present study was that insulin may itself provoke an inflammatory response culminating in diminished hepatic insulin sensitivity. To address this premise, firstly, human cell line U937 differentiated macrophages were exposed to insulin, LPS and PGE2. In these cells, insulin significantly augmented the gene expression of the pro-inflammatory mediators IL-1β, IL-8, CCL2, Oncostatin M (OSM) and microsomal prostaglandin E2 synthase (mPGES1), and of the anti-inflammatory mediator IL-10. Moreover, the synergism between insulin and LPS enhanced the induction provoked by LPS in IL-1β, IL-8, IL-6, CCL2 and TNF-α gene. When combined with PGE2, insulin enhanced the induction provoked by PGE2 in IL-1β, mPGES1 and COX2, and attenuated the inhibition induced by PGE2 in CCL2 and TNF-α gene expression contributing to an enhanced inflammatory response by both mechanisms. Supernatants of insulin-treated U937 macrophages reduced the insulin-dependent induction of glucokinase in hepatocytes by 50%. Cytokines contained in the supernatant of insulin-treated U937 macrophages also activated hepatocytes ERK1/2, resulting in inhibitory serine phosphorylation of the insulin receptor substrate. Additionally, the transcription factor STAT3 was activated by phosphorylation resulting in the induction of SOCS3, which is capable of interrupting the insulin receptor signal chain. MicroRNAs, non-coding RNAs linked to protein expression regulation, nowadays recognized as active players in the generation of several inflammatory disorders such as cancer and type II diabetes are also of interest. Considering that in cancer cachexia, patients are highly affected by insulin resistance and inflammation, control, non-cachectic and cachectic cancer patients were selected and the respective circulating levels of pro-inflammatory mediators and microRNA-21-5p, a posttranscriptional regulator of STAT3 expression, assessed and correlated. Cachectic patients circulating cytokines IL-6 and IL-8 levels were significantly higher than those of non-cachectic and controls, and the expression of microRNA-21-5p was significantly lower. Additionally, microRNA-21-5p reduced expression correlated negatively with IL-6 plasma levels. These results indicate that hyperinsulinemia per se might contribute to the low grade inflammation prevailing in MetS patients and thereby promote the development
of insulin resistance particularly in the liver. Diminished MicroRNA-21-5p expression may enhance inflammation and STAT3 expression in cachectic patients, contributing to the development of insulin resistance.
Change points in time series are perceived as heterogeneities in the statistical or dynamical characteristics of the observations. Unraveling such transitions yields essential information for the understanding of the observed system’s intrinsic evolution and potential external influences. A precise detection of multiple changes is therefore of great importance for various research disciplines, such as environmental sciences, bioinformatics and economics. The primary purpose of the detection approach introduced in this thesis is the investigation of transitions underlying direct or indirect climate observations. In order to develop a diagnostic approach capable to capture such a variety of natural processes, the generic statistical features in terms of central tendency and dispersion are employed in the light of Bayesian inversion. In contrast to established Bayesian approaches to multiple changes, the generic approach proposed in this thesis is not formulated in the framework of specialized partition models of high dimensionality requiring prior specification, but as a robust kernel-based approach of low dimensionality employing least informative prior distributions.
First of all, a local Bayesian inversion approach is developed to robustly infer on the location and the generic patterns of a single transition. The analysis of synthetic time series comprising changes of different observational evidence, data loss and outliers validates the performance, consistency and sensitivity of the inference algorithm. To systematically investigate time series for multiple changes, the Bayesian inversion is extended to a kernel-based inference approach. By introducing basic kernel measures, the weighted kernel inference results are composed into a proxy probability to a posterior distribution of multiple transitions. The detection approach is applied to environmental time series from the Nile river in Aswan and the weather station Tuscaloosa, Alabama comprising documented changes. The method’s performance confirms the approach as a powerful diagnostic tool to decipher multiple changes underlying direct climate observations.
Finally, the kernel-based Bayesian inference approach is used to investigate a set of complex terrigenous dust records interpreted as climate indicators of the African region of the Plio-Pleistocene period. A detailed inference unravels multiple transitions underlying the indirect climate observations, that are interpreted as conjoint changes. The identified conjoint changes coincide with established global climate events. In particular, the two-step transition associated to the establishment of the modern Walker-Circulation contributes to the current discussion about the influence of paleoclimate changes on the environmental conditions in tropical and subtropical Africa at around two million years ago.
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.
Investigation of novel proteins and polysaccharides associated with coccoliths of Emiliania huxleyi
(2016)
Effects of plant community diversity and composition on fungal pathogens in experimental grasslands
(2016)
From dark to light
(2016)
Light-triggered release of bioactive compounds from HA/PLL multilayer films for stimulation of cells
(2016)
The concept of targeting cells and tissues by controlled delivery of molecules is essential in the field of biomedicine. The layer-by-layer (LbL) technology for the fabrication of polymer multilayer films is widely implemented as a powerful tool to assemble tailor-made materials for controlled drug delivery. The LbL films can as well be engineered to act as mimics of the natural cellular microenvironment. Thus, due to the myriad possibilities such as controlled cellular adhesion and drug delivery offered by LbL films, it becomes easily achievable to direct the fate of cells by growing them on the films.
The aim of this work was to develop an approach for non-invasive and precise control of the presentation of bioactive molecules to cells. The strategy is based on employment of the LbL films, which function as support for cells and at the same time as reservoirs for bioactive molecules to be released in a controlled manner. UV light is used to trigger the release of the stored ATP with high spatio-temporal resolution. Both physico-chemical (competitive intermolecular interactions in the film) and biological aspects (cellular response and viability) are addressed in this study.
Biopolymers hyaluronic acid (HA) and poly-L-lysine (PLL) were chosen as the building blocks for the LbL film assembly. Poor cellular adhesion to native HA/PLL films as well as significant degradation by cells within a few days were shown. However, coating the films with gold nanoparticles not only improved cellular adhesion and protected the films from degradation, but also formed a size-exclusion barrier with adjustable cut-off in the size range of a few tens of kDa.
The films were shown to have high reservoir capacity for small charged molecules (reaching mM levels in the film). Furthermore, they were able to release the stored molecules in a sustained manner. The loading and release are explained by a mechanism based on interactions between charges of the stored molecules and uncompensated charges of the biopolymers in the film. Charge balance and polymer dynamics in the film play the pivotal role.
Finally, the concept of light-triggered release from the films has been proven using caged ATP loaded into the films from which ATP was released on demand. ATP induces a fast cellular response, i.e. increase in intracellular [Ca2+], which was monitored in real-time. Limitations of the cellular stimulation by the proposed approach are highlighted by studying the stimulation as a function of irradiation parameters (time, distance, light power). Moreover, caging molecules bind to the film stronger than ATP does, which opens new perspectives for the use of the most diverse chemical compounds as caging molecules.
Employment of HA/PLL films as a nouvelle support for cellular growth and hosting of bioactive molecules, along with the possibility to stimulate individual cells using focused light renders this approach highly efficient and unique in terms of precision and spatio-temporal resolution among those previously described. With its high potential, the concept presented herein provides the foundation for the design of new intelligent materials for single cell studies, with the focus on tissue engineering, diagnostics, and other cell-based applications.
The Milky Way is only one out of billions of galaxies in the universe. However, it is a special galaxy because it allows to explore the main mechanisms involved in its evolution and formation history by unpicking the system star-by-star. Especially, the chemical fingerprints of its stars provide clues and evidence of past events in the Galaxy’s lifetime. These information help not only to decipher the current structure and building blocks of the Milky Way, but to learn more about the general formation process of galaxies.
In the past decade a multitude of stellar spectroscopic Galactic surveys have scanned millions of stars far beyond the rim of the solar neighbourhood. The obtained spectroscopic information provide unprecedented insights to the chemo-dynamics of the Milky Way. In addition analytic models and numerical simulations of the Milky Way provide necessary descriptions and predictions suited for comparison with observations in order to decode the physical properties that underlie the complex system of the Galaxy.
In the thesis various approaches are taken to connect modern theoretical modelling of galaxy formation and evolution with observations from Galactic stellar surveys. With its focus on the chemo-kinematics of the Galactic disk this work aims to determine new observational constraints on the formation of the Milky Way providing also proper comparisons with two different models. These are the population synthesis model TRILEGAL based on analytical distribution functions, which aims to simulate the number and distribution of stars in the Milky Way and its different components, and a hybrid model (MCM) that combines an N-body simulation of a Milky Way like galaxy in the cosmological framework with a semi-analytic chemical evolution model for the Milky Way. The major observational data sets in use come from two surveys, namely the “Radial Velocity Experiment” (RAVE) and the “Sloan Extension for Galactic Understanding and Exploration” (SEGUE).
In the first approach the chemo-kinematic properties of the thin and thick disk of the Galaxy as traced by a selection of about 20000 SEGUE G-dwarf stars are directly compared to the predictions by the MCM model. As a necessary condition for this, SEGUE's selection function and its survey volume are evaluated in detail to correct the spectroscopic observations for their survey specific selection biases. Also, based on a Bayesian method spectro-photometric distances with uncertainties below 15% are computed for the selection of SEGUE G-dwarfs that are studied up to a distance of 3 kpc from the Sun.
For the second approach two synthetic versions of the SEGUE survey are generated based on the above models. The obtained synthetic stellar catalogues are then used to create mock samples best resembling the compiled sample of observed SEGUE G-dwarfs. Generally, mock samples are not only ideal to compare predictions from various models. They also allow validation of the models' quality and improvement as with this work could be especially achieved for TRILEGAL. While TRILEGAL reproduces the statistical properties of the thin and thick disk as seen in the observations, the MCM model has shown to be more suitable in reproducing many chemo-kinematic correlations as revealed by the SEGUE stars. However, evidence has been found that the MCM model may be missing a stellar component with the properties of the thick disk that the observations clearly show. While the SEGUE stars do indicate a thin-thick dichotomy of the stellar Galactic disk in agreement with other spectroscopic stellar studies, no sign for a distinct metal-poor disk is seen in the MCM model.
Usually stellar spectroscopic surveys are limited to a certain volume around the Sun covering different regions of the Galaxy’s disk. This often prevents to obtain a global view on the chemo-dynamics of the Galactic disk. Hence, a suitable combination of stellar samples from independent surveys is not only useful for the verification of results but it also helps to complete the picture of the Milky Way. Therefore, the thesis closes with a comparison of the SEGUE G-dwarfs and a sample of RAVE giants. The comparison reveals that the chemo-kinematic relations agree in disk regions where the samples of both surveys show a similar number of stars. For those parts of the survey volumes where one of the surveys lacks statistics they beautifully complement each other. This demonstrates that the comparison of theoretical models on the one side, and the combined observational data gathered by multiple surveys on the other side, are key ingredients to understand and disentangle the structure and formation history of the Milky Way.
Proteins are natural polypeptides produced by cells; they can be found in both animals and plants, and possess a variety of functions. One of these functions is to provide structural support to the surrounding cells and tissues. For example, collagen (which is found in skin, cartilage, tendons and bones) and keratin (which is found in hair and nails) are structural proteins. When a tissue is damaged, however, the supporting matrix formed by structural proteins cannot always spontaneously regenerate. Tailor-made synthetic polypeptides can be used to help heal and restore tissue formation.
Synthetic polypeptides are typically synthesized by the so-called ring opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCA). Such synthetic polypeptides are generally non-sequence-controlled and thus less complex than proteins. As such, synthetic polypeptides are rarely as efficient as proteins in their ability to self-assemble and form hierarchical or structural supramolecular assemblies in water, and thus, often require rational designing. In this doctoral work, two types of amino acids, γ-benzyl-L/D-glutamate (BLG / BDG) and allylglycine (AG), were selected to synthesize a series of (co)polypeptides of different compositions and molar masses.
A new and versatile synthetic route to prepare polypeptides was developed, and its mechanism and kinetics were investigated. The polypeptide properties were thoroughly studied and new materials were developed from them. In particular, these polypeptides were able to aggregate (or self-assemble) in solution into microscopic fibres, very similar to those formed by collagen. By doing so, they formed robust physical networks and organogels which could be processed into high water-content, pH-responsive hydrogels. Particles with highly regular and chiral spiral morphologies were also obtained by emulsifying these polypeptides. Such polypeptides and the materials derived from them are, therefore, promising candidates for biomedical applications.
Surface-enhanced Raman scattering (SERS) is a promising tool to obtain rich chemical information about analytes at trace levels. However, in order to perform selective experiments on individual molecules, two fundamental requirements have to be fulfilled. On the one hand, areas with high local field enhancement, so-called “hot spots”, have to be created by positioning the supporting metal surfaces in close proximity to each other. In most cases hot spots are formed in the gap between adjacent metal nanoparticles (NPs). On the other hand, the analyte has to be positioned directly in the hot spot in order to profit from the highest signal amplification. The use of DNA origami substrates provides both, the arrangement of AuNPs with nm precision as well as the ability to bind analyte molecules at predefined positions. Consequently, the present cumulative doctoral thesis aims at the development of a novel SERS substrate based on a DNA origami template. To this end, two DNA-functionalized gold nanoparticles (AuNPs) are attached to one DNA origami substrate resulting in the formation of a AuNP dimer and thus in a hot spot within the corresponding gap. The obtained structures are characterized by correlated atomic force microscopy (AFM) and SERS imaging which allows for the combination of structural and chemical information.
Initially, the proof-of principle is presented which demonstrates the potential of the novel approach. It is shown that the Raman signal of 15 nm AuNPs coated with dye-modified DNA
(dye: carboxytetramethylrhodamine (TAMRA)) is significantly higher for AuNP dimers arranged on a DNA origami platform in comparison to single AuNPs. Furthermore, by attaching single TAMRA molecules in the hot spot between two 5 nm AuNPs and optimizing the size of the AuNPs by electroless gold deposition, SERS experiments at the few-molecule level are presented. The initially used DNA origami-AuNPs design is further optimized in many respects. On the one hand, larger AuNPs up to a diameter of 60 nm are used which are additionally treated with a silver enhancement solution to obtain Au-Ag-core-shell NPs. On the other hand, the arrangement of both AuNPs is altered to improve the position of the dye molecule within the hot spot as well as to decrease the gap size between the two particles. With the optimized design the detection of single dye molecules (TAMRA and cyanine 3 (Cy3)) by means of SERS is demonstrated. Quantitatively, enhancement factors up to 10^10 are estimated which is sufficiently high to detect single dye molecules.
In the second part, the influence of graphene as an additional component of the SERS substrate is investigated. Graphene is a two-dimensional material with an outstanding combination of electronical, mechanical and optical properties. Here, it is demonstrated that
single layer graphene (SLG) replicates the shape of underlying non-modified DNA origami
substrates very well, which enables the monitoring of structural alterations by AFM imaging.
In this way, it is shown that graphene encapsulation significantly increases the structural
stability of bare DNA origami substrates towards mechanical force and prolonged exposure
to deionized water.
Furthermore, SLG is used to cover DNA origami substrates which are functionalized with a
40 nm AuNP dimer. In this way, a novel kind of hybrid material is created which exhibits
several advantages compared to the analogue non-covered SERS substrates. First, the fluorescence background of dye molecules that are located in between the AuNP surface and SLG is efficiently reduced. Second, the photobleaching rate of the incorporated dye molecules is decreased up to one order of magnitude. Third, due to the increased photostability of the investigated dye molecules, the performance of polarization-dependent series measurements on individual structures is enabled. This in turn reveals extensive information about the dye molecules in the hot spot as well as about the strain induced within the graphene lattice.
Although SLG can significantly influence the SERS substrate in the aforementioned ways, all
those effects are strongly related to the extent of contact with the underlying AuNP dimer.
Ionothermal carbon materials
(2016)
Alternative concepts for energy storage and conversion have to be developed, optimized and employed to fulfill the dream of a fossil-independent energy economy. Porous carbon materials play a major role in many energy-related devices. Among different characteristics, distinct porosity features, e.g., specific surface area (SSA), total pore volume (TPV), and the pore size distribution (PSD), are important to maximize the performance in the final device. In order to approach the aim to synthesize carbon materials with tailor-made porosity in a sustainable fashion, the present thesis focused on biomass-derived precursors employing and developing the ionothermal carbonization.
During the ionothermal carbonization, a salt melt simultaneously serves as solvent and porogen. Typically, eutectic mixtures containing zinc chloride are employed as salt phase. The first topic of the present thesis addressed the possibility to precisely tailor the porosity of ionothermal carbon materials by an experimentally simple variation of the molar composition of the binary salt mixture. The developed pore tuning tool allowed the synthesis of glucose derived carbon materials with predictable SSAs in the range of ~ 900 to ~ 2100 m2 g-1. Moreover, the nucleobase adenine was employed as precursor introducing nitrogen functionalities in the final material. Thereby, the chemical properties of the carbon materials are varied leading to new application fields. Nitrogen doped carbons (NDCs) are able to catalyze the oxygen reduction reaction (ORR) which takes place on the cathodic site of a fuel cell. The herein developed porosity tailoring allowed the synthesis of adenine derived NDCs with outstanding SSAs of up to 2900 m2 g-1 and very large TPV of 5.19 cm3 g-1. Furthermore, the influence of the porosity on the ORR could be directly investigated enabling the precise optimization of the porosity characteristics of NDCs for this application. The second topic addressed the development of a new method to investigate the not-yet unraveled mechanism of the oxygen reduction reaction using a rotating disc electrode setup. The focus was put on noble-metal free catalysts. The results showed that the reaction pathway of the investigated catalysts is pH-dependent indicating different active species at different pH-values. The third topic addressed the expansion of the used salts for the ionothermal approach towards hydrated calcium and magnesium chloride. It was shown that hydrated salt phases allowed the introduction of a secondary templating effect which was connected to the coexistence of liquid and solid salt phases. The method enabled the synthesis of fibrous NDCs with SSAs of up to 2780 m2 g-1 and very large TPV of 3.86 cm3 g-1. Moreover, the concept of active site implementation by a facile low-temperature metalation employing the obtained NDCs as solid ligands could be shown for the first time in the context of ORR.
Overall, the thesis may pave the way towards highly porous carbon with tailor-made porosity materials prepared by an inexpensive and sustainable pathway, which can be applied in energy related field thereby supporting the needed expansion of the renewable energy sector.
In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes.
The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC–Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer.
The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts.
En route towards advanced catalyst materials for the electrocatalytic water splitting reaction
(2016)
The thesis on hand deals with the development of new types of catalysts based on pristine metals and ceramic materials and their application as catalysts for the electrocatalytic water splitting reaction. In order to breathe life into this technology, cost-efficient, stable and efficient catalysts are imploringly desired. In this manner, the preparation of Mn-, N-, S-, P-, and C-containing nickel materials has been investigated together with the theoretical and electrochemical elucidation of their activity towards the hydrogen (and oxygen) evolution reaction. The Sabatier principle has been used as the principal guideline towards successful tuning of catalytic sites. Furthermore, two pathways have been chosen to ameliorate the electrocatalytic performance, namely, the direct improvement of intrinsic properties through appropriate material selection and secondly the increase of surface area of the catalytic material with an increased amount of active sites. In this manner, bringing materials with optimized hydrogen adsorption free energy onto high surface area support, catalytic performances approaching the golden standards of noble metals were feasible. Despite varying applied synthesis strategies (wet chemistry in organic solvents, ionothermal reaction, gas phase reaction), one goal has been systematically pursued: to understand the driving mechanism of the growth. Moreover, deeper understanding of inherent properties and kinetic parameters of the catalytic materials has been gained.
Eye movements serve as a window into ongoing visual-cognitive processes and can thus be used to investigate how people perceive real-world scenes. A key issue for understanding eye-movement control during scene viewing is the roles of central and peripheral vision, which process information differently and are therefore specialized for different tasks (object identification and peripheral target selection respectively). Yet, rather little is known about the contributions of central and peripheral processing to gaze control and how they are coordinated within a fixation during scene viewing. Additionally, the factors determining fixation durations have long been neglected, as scene perception research has mainly been focused on the factors determining fixation locations. The present thesis aimed at increasing the knowledge on how central and peripheral vision contribute to spatial and, in particular, to temporal aspects of eye-movement control during scene viewing. In a series of five experiments, we varied processing difficulty in the central or the peripheral visual field by attenuating selective parts of the spatial-frequency spectrum within these regions. Furthermore, we developed a computational model on how foveal and peripheral processing might be coordinated for the control of fixation duration. The thesis provides three main findings. First, the experiments indicate that increasing processing demands in central or peripheral vision do not necessarily prolong fixation durations; instead, stimulus-independent timing is adapted when processing becomes too difficult. Second, peripheral vision seems to play a prominent role in the control of fixation durations, a notion also implemented in the computational model. The model assumes that foveal and peripheral processing proceed largely in parallel and independently during fixation, but can interact to modulate fixation duration. Thus, we propose that the variation in fixation durations can in part be accounted for by the interaction between central and peripheral processing. Third, the experiments indicate that saccadic behavior largely adapts to processing demands, with a bias of avoiding spatial-frequency filtered scene regions as saccade targets. We demonstrate that the observed saccade amplitude patterns reflect corresponding modulations of visual attention. The present work highlights the individual contributions and the interplay of central and peripheral vision for gaze control during scene viewing, particularly for the control of fixation duration. Our results entail new implications for computational models and for experimental research on scene perception.
The aim of this thesis was the elucidation of different ionization methods (resonance-enhanced multiphoton ionization – REMPI, electrospray ionization – ESI, atmospheric pressure chemical ionization – APCI) in ion mobility (IM) spectrometry. In order to gain a better understanding of the ionization processes, several spectroscopic, mass spectrometric and theoretical methods were also used. Another focus was the development of experimental techniques, including a high resolution spectrograph and various combinations of IM and mass spectrometry.
The novel high resolution 2D spectrograph facilitates spectroscopic resolutions in the range of commercial echelle spectrographs. The lowest full width at half maximum of a peak achieved was 25 pm. The 2D spectrograph is based on the wavelength separation of light by the combination of a prism and a grating in one dimension, and an etalon in the second dimension. This instrument was successfully employed for the acquisition of Raman and laser-induced breakdown spectra.
Different spectroscopic methods (light scattering and fluorescence spectroscopy) permitting a spatial as well as spectral resolution, were used to investigate the release of ions in the electrospray. The investigation is based on the 50 nm shift of the fluorescence band of rhodamine 6G ions of during the transfer from the electrospray droplets to the gas phase.
A newly developed ionization chamber operating at reduced pressure (0.5 mbar) was coupled to a time-of-flight mass spectrometer. After REMPI of H2S, an ionization chemistry analogous to H2O was observed with this instrument. Besides H2S+ and its fragments, H3S+ and protonated analyte ions could be observed as a result of proton-transfer reactions.
For the elucidation of the peaks in IM spectra, a combination of IM spectrometer and linear quadrupole ion trap mass spectrometer was developed. The instrument can be equipped with various ionization sources (ESI, REMPI, APCI) and was used for the characterization of the peptide bradykinin and the neuroleptic promazine.
The ionization of explosive compounds in an APCI source based on soft x-radiation was investigated in a newly developed ionization chamber attached to the ion trap mass spectrometer. The major primary and secondary reactions could be characterized and explosive compound ions could be identified and assigned to the peaks in IM spectra. The assignment is based on the comparison of experimentally determined and calculated IM. The methods of calculation currently available exhibit large deviations, especially in the case of anions. Therefore, on the basis of an assessment of available methods, a novel hybrid method was developed and characterized.
Buyer-seller negotiations have significant impact on a company’s profitability, which makes practitioners aim at maximizing their performance. One lever for increasing bargaining performance is to pursue a clearly defined aspiration, i.e. one’s most desired outcome. In this context, the author explores the role of such aspirations in the three negotiation phases: preparation, bargaining, and striking a deal. She investigates determinants of aspirations, unintended consequences such as unethical bargaining behavior, and the consequences of overly ambitious aspirations. As a result, she does not only close existing gaps in negotiation research, but also derives valuable implications for practitioners
Foam fractionation of surfactant and protein solutions is a process dedicated to separate surface active molecules from each other due to their differences in surface activities. The process is based on forming bubbles in a certain mixed solution followed by detachment and rising of bubbles through a certain volume of this solution, and consequently on the formation of a foam layer on top of the solution column. Therefore, systematic analysis of this whole process comprises of at first investigations dedicated to the formation and growth of single bubbles in solutions, which is equivalent to the main principles of the well-known bubble pressure tensiometry. The second stage of the fractionation process includes the detachment of a single bubble from a pore or capillary tip and its rising in a respective aqueous solution. The third and final stage of the process is the formation and stabilization of the foam created by these bubbles, which contains the adsorption layers formed at the growing bubble surface, carried up and gets modified during the bubble rising and finally ends up as part of the foam layer.
Bubble pressure tensiometry and bubble profile analysis tensiometry experiments were performed with protein solutions at different bulk concentrations, solution pH and ionic strength in order to describe the process of accumulation of protein and surfactant molecules at the bubble surface. The results obtained from the two complementary methods allow understanding the mechanism of adsorption, which is mainly governed by the diffusional transport of the adsorbing protein molecules to the bubble surface. This mechanism is the same as generally discussed for surfactant molecules. However, interesting peculiarities have been observed for protein adsorption kinetics at sufficiently short adsorption times. First of all, at short adsorption times the surface tension remains constant for a while before it decreases as expected due to the adsorption of proteins at the surface. This time interval is called induction time and it becomes shorter with increasing protein bulk concentration. Moreover, under special conditions, the surface tension does not stay constant but even increases over a certain period of time. This so-called negative surface pressure was observed for BCS and BLG and discussed for the first time in terms of changes in the surface conformation of the adsorbing protein molecules. Usually, a negative surface pressure would correspond to a negative adsorption, which is of course impossible for the studied protein solutions. The phenomenon, which amounts to some mN/m, was rather explained by simultaneous changes in the molar area required by the adsorbed proteins and the non-ideality of entropy of the interfacial layer. It is a transient phenomenon and exists only under dynamic conditions.
The experiments dedicated to the local velocity of rising air bubbles in solutions were performed in a broad range of BLG concentration, pH and ionic strength. Additionally, rising bubble experiments were done for surfactant solutions in order to validate the functionality of the instrument. It turns out that the velocity of a rising bubble is much more sensitive to adsorbing molecules than classical dynamic surface tension measurements. At very low BLG or surfactant concentrations, for example, the measured local velocity profile of an air bubble is changing dramatically in time scales of seconds while dynamic surface tensions still do not show any measurable changes at this time scale. The solution’s pH and ionic strength are important parameters that govern the measured rising velocity for protein solutions. A general theoretical description of rising bubbles in surfactant and protein solutions is not available at present due to the complex situation of the adsorption process at a bubble surface in a liquid flow field with simultaneous Marangoni effects. However, instead of modelling the complete velocity profile, new theoretical work has been started to evaluate the maximum values in the profile as characteristic parameter for dynamic adsorption layers at the bubble surface more quantitatively.
The studies with protein-surfactant mixtures demonstrate in an impressive way that the complexes formed by the two compounds change the surface activity as compared to the original native protein molecules and therefore lead to a completely different retardation behavior of rising bubbles. Changes in the velocity profile can be interpreted qualitatively in terms of increased or decreased surface activity of the formed protein-surfactant complexes. It was also observed that the pH and ionic strength of a protein solution have strong effects on the surface activity of the protein molecules, which however, could be different on the rising bubble velocity and the equilibrium adsorption isotherms. These differences are not fully understood yet but give rise to discussions about the structure of protein adsorption layer under dynamic conditions or in the equilibrium state.
The third main stage of the discussed process of fractionation is the formation and characterization of protein foams from BLG solutions at different pH and ionic strength. Of course a minimum BLG concentration is required to form foams. This minimum protein concentration is a function again of solution pH and ionic strength, i.e. of the surface activity of the protein molecules. Although at the isoelectric point, at about pH 5 for BLG, the hydrophobicity and hence the surface activity should be the highest, the concentration and ionic strength effects on the rising velocity profile as well as on the foamability and foam stability do not show a maximum. This is another remarkable argument for the fact that the interfacial structure and behavior of BLG layers under dynamic conditions and at equilibrium are rather different. These differences are probably caused by the time required for BLG molecules to adapt respective conformations once they are adsorbed at the surface.
All bubble studies described in this work refer to stages of the foam fractionation process. Experiments with different systems, mainly surfactant and protein solutions, were performed in order to form foams and finally recover a solution representing the foamed material. As foam consists to a large extent of foam lamella – two adsorption layers with a liquid core – the concentration in a foamate taken from foaming experiments should be enriched in the stabilizing molecules. For determining the concentration of the foamate, again the very sensitive bubble rising velocity profile method was applied, which works for any type of surface active materials. This also includes technical surfactants or protein isolates for which an accurate composition is unknown.
Porous Membranes from Imidazolium- and Pyridinium-based Poly(ionic liquid)s with Targeted Properties
(2016)
We do magnetohydrodynamic (MHD) simulations of local box models of turbulent Interstellar Medium (ISM) and analyse the process of amplification and saturation of mean magnetic fields with methods of mean field dynamo theory. It is shown that the process of saturation of mean fields can be partially described by the prolonged diffusion time scales in presence of the dynamically significant magnetic fields. However, the outward wind also plays an essential role in the saturation in higher SN rate case. Algebraic expressions for the back reaction of the magnetic field onto the turbulent transport coefficients are derived, which allow a complete description of the nonlinear dynamo. We also present the effects of dynamically significant mean fields on the ISM configuration and pressure distribution. We further add the cosmic ray component in the simulations and investigate the kinematic growth of mean fields with a dynamo perspective.
While children acquire new words and simple sentence structures extremely fast and without much effort, the ability to process complex sentences develops rather late in life. Although the conjoint occurrence between brain-structural and brain-functional changes, the decrease of plasticity, and changes in cognitive abilities suggests a certain causality between these processes, concrete evidence for the relation between brain development, language processing, and language performance is rare. Therefore, the current dissertation investigates the tripartite relationship between behavior (in the form of language performance and cognitive maturation as prerequisite for language processing), brain structure (in the form of gray matter maturation), and brain function (in the form of brain activation evoked by complex sentence processing). Previous developmental studies indicate a missing increase of activation in accordance to sentence complexity (functional selectivity) in language-relevant brain areas in children. To determine the factors contributing to the functional development of language-relevant brain areas, different methodologies and data acquisition techniques were used to investigate the processing of center-embedded sentences in 5- and 6-year-old children, 7- and 8-year-old children, and adults. Behavioral results indicate that children between 5 and 8 years show difficulties in processing double embedded sentences and that their performance for these type of sentences is positively correlated with digit span. In 7- and 8-year-old children, it was found that especially the processing of long-distance relations between the initial phrase and its corresponding verb appears to be associated with the subject’s verbal working memory capacity. In contrast, children’s performance for double embedded sentences in the younger age group positively correlated with their performance in a standardized sentence comprehension test. This finding supports the hypothesis that processing difficulties in this age group may be mainly attributed to difficulties in processing case marking information. These findings are discussed with respect to current accounts of language and working memory development. A second study aimed at investigating the structural maturation of brain areas involved in sentence comprehension. To do this, whole-brain magnetic resonance images from 59 children between 5 and 8 years were collected and children’s gray matter was analyzed by using voxel-based morphometry. Children’s grammatical proficiency was assessed by a standardized sentence comprehension test. A confirmatory factory analysis corroborated a grammar-relevant and a verbal working memory-relevant factor underlying the measured performance. While children’s ability to assign thematic roles is positively correlated with gray matter probability (GMP) in the left inferior temporal gyrus and the left inferior frontal gyrus, verbal working memory-related performance is positively correlated with GMP in the left parietal operculum extending into the posterior superior temporal gyrus. These areas have been previously shown to be differentially engaged in adults’ complex sentence processing. Thus, the findings of the second study suggest a specific correspondence between children’s GMP in language-relevant brain regions and differential cognitive abilities which underlie complex sentence comprehension. In a third study, functional brain activity during the processing of center-embedded sentences was investigated in three different age groups (5–6 years, 7–8 years, and adults). Although all age groups engage a qualitatively comparable network of the left pars opercularis (PO), the left inferior parietal lobe extending into the posterior superior temporal gyrus (IPL/pSTG), the supplementary motor area (SMA) and the cerebellum, functional selectivity of these regions was only observable in adults. However, functional activation of the language-related regions (PO and IPL/pSTG) predicted sentence comprehension performance for all age groups. To solve the question of the complex interplay between different maturational factors, a fourth study analyzed the predictive power of gray matter probability, verbal working memory capacity, and behavioral differences in performance for simple and complex sentence for the functional selectivity of each activated region. These analyses revealed that the establishment of the adult-like functional selectivity for complex sentences is predicted by a reduction of the left PO’s gray matter probability across age groups while that of the IPL/pSTG is additionally predicted by verbal working memory capacity. Taken all findings together, the current thesis provides evidence that both structural brain maturation and verbal working memory expansion provide the basis for the emergence of functional selectivity in language-related brain regions leading to more efficient sentence processing during development.
The author examines the cultural identity development of Oromo-Americans in Minnesota, an ethnic group originally located within the national borders of Ethiopia. Earlier studies on language and cultural identity have shown that the degree of ethnic orientation of minorities commonly decreases from generation to generation. Yet oppression and a visible minority status were identified as factors delaying the process of de-ethnicization. Given that Oromos fled persecution in Ethiopia and are confronted with the ramifications of a visible minority status in the U.S., it can be expected that they have retained strong ties to their ethnic culture. This study, however, came to a more complex and theory-building result.
Exhaustivity
(2016)
The dissertation proposes an answer to the question of how to model exhaustive inferences and what the meaning of the linguistic material that triggers these inferences is. In particular, it deals with the semantics of exclusive particles, clefts, and progressive aspect in Ga, an under-researched language spoken in Ghana. Based on new data coming from the author’s original fieldwork in Accra, the thesis points to a previously unattested variation in the semantics of exclusives in a cross-linguistic perspective, analyzes the connections between exhaustive interpretation triggered by clefts and the aspectual interpretation of the sentence, and identifies a cross-categorial definite determiner. By that it sheds new light on several exhaustivity-related phenomena in both the nominal and the verbal domain and shows that both domains are closely connected.
Dietary approaches contribute to the prevention and treatment of type 2 diabetes. High protein diets were shown to exert beneficial as well as adverse effects on metabolism. However, it is unclear whether the protein origin plays a role in these effects. The LeguAN study investigated in detail the effects of two high protein diets, either from plant or animal origin, in type 2 diabetic patients. Both diets contained 30 EN% protein, 40 EN% carbohydrates, and 30 EN% fat. Fiber content, glycemic index, and composition of dietary fats were similar in both diets. In comparison to previous dietary habits, the fat content was exchanged for protein, while the carbohydrate intake was not modified. Overall, both high protein diets led to improvements of glycemic control, insulin sensitivity, liver fat, and cardiovascular risk markers without remarkable differences between the protein types.
Fasting glucose together with indices of insulin resistance were ameliorated by both interventions to varying extents but without significant differences between protein types. The decline of HbA1c was more pronounced in the plant protein group, whereby the improvement of insulin sensitivity in the animal protein group. The high protein intake had only slight influence on postprandial metabolism seen for free fatty acids and indices of insulin secretion, sensitivity and degradation. Except for GIP release, ingestion of animal and plant meals did not provoke differential metabolic and hormonal responses despite diverse circulating amino acid levels.
The animal protein diets led to a selective increase of fat-free mass and decrease of total fat mass, which was not significantly different from the plant protein diet. Moreover, the high protein diets potently decreased liver fat content by 42% on average which was linked to significantly diminished lipogenesis, free fatty acids flux and lipolysis in adipose tissue. Moderate decline of circulating liver enzymes was induced by both interventions. The liver fat reduction was associated with improved glucose homeostasis and insulin sensitivity which underlines the protective effect of the diets.
Blood lipid profile improved in all subjects and was probably related to the lower fat intake. Reductions in uric acid and markers of inflammation further argued for metabolic benefits of both high protein diets. Systolic and diastolic blood pressure declined only in the PP group pointing a possible role of arginine.
Kidney function was not altered by high protein consumption over 6 weeks. The rapid decrease of serum creatinine in the PP group was noteworthy and should be further investigated. Protein type did not seem to play a role but long-term studies are warranted to fully elucidate safety of high protein regimen.
Varying the source of dietary proteins did not affect the mTOR pathway in adipose tissue and blood cells under neither acute nor chronic settings. Enhancement of whole-body insulin sensitivity suggested also no alteration of mTOR and no impairment of insulin sensitivity in skeletal muscle.
A remarkable outcome was the extensive reduction of FGF21, critical regulator of metabolic processes, by approximately 50% independently of protein type. Whether hepatic ER-stress, ammonia flux or rather macronutrient preferences is behind this paradoxical finding remains to be investigated in detail.
Unlike initial expectations and previous reports plant protein based diet had no clear advantage over animal proteins. The pronounced beneficial effect of animal protein on insulin homeostasis despite high BCAA and methionine intake was certainly unexpected assuming more complex metabolic adaptations occurring upon prolonged consumption. In addition, the reduced fat intake may have also contributed to the overall improvements in both groups.
Taking into account the above observed study results, a short-term diet containing 30 EN% protein (either from plant or animal origin), 40 EN% carbohydrates, and 30 EN% fat with lower SFA amount leads to metabolic improvements in diabetic patients, regardless of protein source.