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The advantages of remote sensing using Unmanned Aerial Vehicles (UAVs) are a high spatial resolution of images, temporal flexibility and narrow-band spectral data from different wavelengths domains. This enables the detection of spatio-temporal dynamics of environmental variables, like plant-related carbon dynamics in agricultural landscapes. In this paper, we quantify spatial patterns of fresh phytomass and related carbon (C) export using imagery captured by a 12-band multispectral camera mounted on the fixed wing UAV Carolo P360. The study was performed in 2014 at the experimental area CarboZALF-D in NE Germany. From radiometrically corrected and calibrated images of lucerne (Medicago sativa), the performance of four commonly used vegetation indices (VIs) was tested using band combinations of six near-infrared bands. The highest correlation between ground-based measurements of fresh phytomass of lucerne and VIs was obtained for the Enhanced Vegetation Index (EVI) using near-infrared band b(899). The resulting map was transformed into dry phytomass and finally upscaled to total C export by harvest. The observed spatial variability at field- and plot-scale could be attributed to small-scale soil heterogeneity in part.
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.
The synthesis and photophysical properties of two new FRET pairs based on coumarin as a donor and DBD dye as an acceptor are described. The introduction of a bromo atom dramatically increases the two-photon excitation (2PE) cross section providing a 2PE-FRET system, which is also suitable for 2PE-FLIM.
The synthesis and photophysical properties of two new FRET pairs based on coumarin as a donor and DBD dye as an acceptor are described. The introduction of a bromo atom dramatically increases the two-photon excitation (2PE) cross section providing a 2PE-FRET system, which is also suitable for 2PE-FLIM.
Background. The bay cat Catopuma badia is endemic to Borneo, whereas its sister species the Asian golden cat Catopuma temminckii is distributed from the Himalayas and southern China through Indochina, Peninsular Malaysia and Sumatra. Based onmorphological data, up to five subspecies of the Asian golden cat have been recognized, but a taxonomic assessment, including molecular data and morphological characters, is still lacking. Results. We combined molecular data (whole mitochondrial genomes), morphological data (pelage) and species distribution projections (up to the Late Pleistocene) to infer how environmental changes may have influenced the distribution of these sister species over the past 120 000 years. The molecular analysis was based on sequenced mitogenomes of 3 bay cats and 40 Asian golden cats derived mainly from archival samples. Our molecular data suggested a time of split between the two species approximately 3.16 Ma and revealed very low nucleotide diversity within the Asian golden cat population, which supports recent expansion of the population. Discussion. The low nucleotide diversity suggested a population bottleneck in the Asian golden cat, possibly caused by the eruption of the Toba volcano in Northern Sumatra (approx. 74 kya), followed by a continuous population expansion in the Late Pleistocene/Early Holocene. Species distribution projections, the reconstruction of the demographic history, a genetic isolation-by-distance pattern and a gradual variation of pelage pattern support the hypothesis of a post-Toba population expansion of the Asian golden cat from south China/Indochina to PeninsularMalaysia and Sumatra. Our findings reject the current classification of five subspecies for the Asian golden cat, but instead support either a monotypic species or one comprising two subspecies: (i) the Sunda golden cat, distributed south of the Isthmus of Kra: C. t. temminckii and (ii) Indochinese, Indian, Himalayan and Chinese golden cats, occurring north of the Isthmus: C. t. moormensis.
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.
Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach. With multi-angle dynamic light scattering, asymmetrical flow field-flow fractionation, gel electrophoresis, and liquid chromatography-mass spectrometry, it is demonstrated that protein adsorption on PEtOxylated nanoparticles is extremely low, similar as on PEGylated nanoparticles. Moreover, quantitative microscopy reveals that PEtOxylation significantly reduces the non-specific cellular uptake, particularly by macrophage-like cells. Collectively, studies demonstrate that PEtOx is a very effective alternative to PEG for stealth modification of the surface of nanoparticles.
Billions of Linked Data triples exist in thousands of RDF knowledge graphs on the Web, but few of those graphs can be queried live from Web applications. Only a limited number of knowledge graphs are available in a queryable interface, and existing interfaces can be expensive to host at high availability. To mitigate this shortage of live queryable Linked Data, we designed a low-cost Triple Pattern Fragments interface for servers, and a client-side algorithm that evaluates SPARQL queries against this interface. This article describes the Linked Data Fragments framework to analyze Web interfaces to Linked Data and uses this framework as a basis to define Triple Pattern Fragments. We describe client-side querying for single knowledge graphs and federations thereof. Our evaluation verifies that this technique reduces server load and increases caching effectiveness, which leads to lower costs to maintain high server availability. These benefits come at the expense of increased bandwidth and slower, but more stable query execution times. These results substantiate the claim that lightweight interfaces can lower the cost for knowledge publishers compared to more expressive endpoints, while enabling applications to query the publishers’ data with the necessary reliability.
Exploring generalisation following treatment of language deficits in aphasia can provide insights into the functional relation of the cognitive processing systems involved. In the present study, we first review treatment outcomes of interventions targeting sentence processing deficits and, second report a treatment study examining the occurrence of practice effects and generalisation in sentence comprehension and production. In order to explore the potential linkage between processing systems involved in comprehending and producing sentences, we investigated whether improvements generalise within (i.e., uni-modal generalisation in comprehension or in production) and/or across modalities (i.e., cross-modal generalisation from comprehension to production or vice versa). Two individuals with aphasia displaying co-occurring deficits in sentence comprehension and production were trained on complex, non-canonical sentences in both modalities. Two evidence-based treatment protocols were applied in a crossover intervention study with sequence of treatment phases being randomly allocated. Both participants benefited significantly from treatment, leading to uni-modal generalisation in both comprehension and production. However, cross-modal generalisation did not occur. The magnitude of uni-modal generalisation in sentence production was related to participants’ sentence comprehension performance prior to treatment. These findings support the assumption of modality-specific sub-systems for sentence comprehension and production, being linked uni-directionally from comprehension to production.
Exploring generalisation following treatment of language deficits in aphasia can provide insights into the functional relation of the cognitive processing systems involved. In the present study, we first review treatment outcomes of interventions targeting sentence processing deficits and, second report a treatment study examining the occurrence of practice effects and generalisation in sentence comprehension and production. In order to explore the potential linkage between processing systems involved in comprehending and producing sentences, we investigated whether improvements generalise within (i.e., uni-modal generalisation in comprehension or in production) and/or across modalities (i.e., cross-modal generalisation from comprehension to production or vice versa). Two individuals with aphasia displaying co-occurring deficits in sentence comprehension and production were trained on complex, non-canonical sentences in both modalities. Two evidence-based treatment protocols were applied in a crossover intervention study with sequence of treatment phases being randomly allocated. Both participants benefited significantly from treatment, leading to uni-modal generalisation in both comprehension and production. However, cross-modal generalisation did not occur. The magnitude of uni-modal generalisation in sentence production was related to participants’ sentence comprehension performance prior to treatment. These findings support the assumption of modality-specific sub-systems for sentence comprehension and production, being linked uni-directionally from comprehension to production.
Objective: To estimate the prevalence and the type of antidepressant medication prescribed by German psychiatrists to patients with depression and cardiovascular diseases (CVD). Methods: This study was a retrospective database analysis in Germany using the Disease Analyzer Database (IMS Health, Germany). The study population included 2,288 CVD patients between 40 and 90 years of age from 175 psychiatric practices. The observation period was between 2004 and 2013. Follow-up lasted up to 12 months and ended in April 2015. Also included were 2,288 non-CVD controls matched (1 : 1) to CVD cases on the basis of age, gender, health insurance coverage, depression severity, and diagnosing physician. Results: Mean age was 68.6 years. 46.2% of patients were men, and 5.9% had private health insurance coverage. Mild, moderate, or severe depression was present in 18.7%, 60.7%, and 20.6% of patients, respectively. Most patients had treatment within a year, many of them immediately after depression diagnosis. Patients with moderate and severe depression were more likely to receive treatment than patients with mild depression. There was no difference between CVD and non-CVD in the proportion of patients treated. Nonetheless, CVD patients received selective serotonin reuptake inhibitors / serotonin-noradrenaline reuptake inhibitors (SSRIs/SNRIs) significantly more frequently. Conversely, patients without CVD were more often treated with TCA. Conclusion: There was no association between CVD and the initiation of depression treatment. Furthermore, CVD patients received SSRIs/SNRIs more frequently.
This article assesses the distance between the laws of stochastic differential equations with multiplicative Lévy noise on path space in terms of their characteristics. The notion of transportation distance on the set of Lévy kernels introduced by Kosenkova and Kulik yields a natural and statistically tractable upper bound on the noise sensitivity. This extends recent results for the additive case in terms of coupling distances to the multiplicative case. The strength of this notion is shown in a statistical implementation for simulations and the example of a benchmark time series in paleoclimate.
Context. Supernova remnants are known as sources of Galactic cosmic rays for their nonthermal emission of radio waves, X-rays, and gamma rays. However, the observed soft broken power-law spectra are hard to reproduce within standard acceleration theory based on the assumption of Bohm diffusion and steady-state calculations. Aims. We point out that a time-dependent treatment of the acceleration process together with a self-consistent treatment of the scattering turbulence amplification is necessary. Methods. We numerically solve the coupled system of transport equations for cosmic rays and isotropic Alfvenic turbulence. The equations are coupled through the growth rate of turbulence determined by the cosmic-ray gradient and the spatial diffusion coefficient of cosmic rays determined by the energy density of the turbulence. The system is solved on a comoving expanding grid extending upstream for dozens of shock radii, allowing for the self-consistent study of cosmic-ray diffusion in the vicinity of their acceleration site. The transport equation for cosmic rays is solved in a test-particle approach. Results. We demonstrate that the system is typically not in a steady state. In fact, even after several thousand years of evolution, no equilibrium situation is reached. The resulting time-dependent particle spectra strongly differ from those derived assuming a steady state and Bohm diffusion. Our results indicate that proper accounting for the evolution of the scattering turbulence and hence the particle diffusion coefficient is crucial for the formation of the observed soft spectra. In any case, the need to continuously develop magnetic turbulence upstream of the shock introduces nonlinearity in addition to that imposed by cosmic-ray feedback.
This article rests on the assumption of the “complexity, messiness, power relations, and contested character of the contemporary dualistic system,” which comprises great powers and “superimposed, functionally differentiated global subsystems of world society” (Cohen 2012:5). The article argues that this framework is being shaped by the current transition of global order. In turn, this raises the question how the state-led negotiation of today's order transition can be understood against the backdrop of a post-Westphalian environment. The article challenges the widespread argument pertaining to the “autonomy of transnational actors” by suggesting that the influence of nonstate actors is dependent on a particular institutional context in which the key political questions framing a social order are settled. Whereas research on international institutions and their design simply assumes that this is the case, here it is argued that unless these framing patterns are agreed upon by major powers, the respective order and its elements, that is, institutions and regimes, remain contested or deadlocked. When this happens, the political impact of non-state actors is largely neutralized or strongly weakened and their effective autonomy from great powers is minimized.
Transmorphic
(2016)
Defining Graphical User Interfaces (GUIs) through functional abstractions can reduce the complexity that arises from mutable abstractions. Recent examples, such as Facebook's React GUI framework have shown, how modelling the view as a functional projection from the application state to a visual representation can reduce the number of interacting objects and thus help to improve the reliabiliy of the system. This however comes at the price of a more rigid, functional framework where programmers are forced to express visual entities with functional abstractions, detached from the way one intuitively thinks about the physical world.
In contrast to that, the GUI Framework Morphic allows interactions in the graphical domain, such as grabbing, dragging or resizing of elements to evolve an application at runtime, providing liveness and directness in the development workflow. Modelling each visual entity through mutable abstractions however makes it difficult to ensure correctness when GUIs start to grow more complex. Furthermore, by evolving morphs at runtime through direct manipulation we diverge more and more from the symbolic description that corresponds to the morph. Given that both of these approaches have their merits and problems, is there a way to combine them in a meaningful way that preserves their respective benefits?
As a solution for this problem, we propose to lift Morphic's concept of direct manipulation from the mutation of state to the transformation of source code. In particular, we will explore the design, implementation and integration of a bidirectional mapping between the graphical representation and a functional and declarative symbolic description of a graphical user interface within a self hosted development environment. We will present Transmorphic, a functional take on the Morphic GUI Framework, where the visual and structural properties of morphs are defined in a purely functional, declarative fashion. In Transmorphic, the developer is able to assemble different morphs at runtime through direct manipulation which is automatically translated into changes in the code of the application. In this way, the comprehensiveness and predictability of direct manipulation can be used in the context of a purely functional GUI, while the effects of the manipulation are reflected in a medium that is always in reach for the programmer and can even be used to incorporate the source transformations into the source files of the application.
Responses to pathogens, including host transcriptional reprogramming, require partially antagonistic signalling pathways dependent on the phytohormones salicylic (SA) and jasmonic (JA) acids. However, upstream factors modulating the interplay of these pathways are not well characterized. Here, we identify the transcription factor ANAC032 from Arabidopsis thaliana as one such regulator in response to the bacterial pathogen Pseudomonas syringae pv. tomato DC3000 (Pst). ANAC032 directly represses MYC2 activation upon Pst attack, resulting in blockage of coronatine-mediated stomatal reopening which restricts entry of bacteria into plant tissue. Furthermore, ANAC032 activates SA signalling by repressing NIMIN1, a key negative regulator of SA-dependent defence. Finally, ANAC032 reduces expression of JA-responsive genes, including PDF1.2A. Thus, ANAC032 enhances resistance to Pst by generating an orchestrated transcriptional output towards key SA- and JA-signalling genes coordinated through direct binding of ANAC032 to the MYC2, NIMIN1 and PDF1.2A promoters.
Species can adjust their traits in response to selection which may strongly influence species coexistence. Nevertheless, current theory mainly assumes distinct and time-invariant trait values. We examined the combined effects of the range and the speed of trait adaptation on species coexistence using an innovative multispecies predator–prey model. It allows for temporal trait changes of all predator and prey species and thus simultaneous coadaptation within and among trophic levels. We show that very small or slow trait adaptation did not facilitate coexistence because the stabilizing niche differences were not sufficient to offset the fitness differences. In contrast, sufficiently large and fast trait adaptation jointly promoted stable or neutrally stable species coexistence. Continuous trait adjustments in response to selection enabled a temporally variable convergence and divergence of species traits; that is, species became temporally more similar (neutral theory) or dissimilar (niche theory) depending on the selection pressure, resulting over time in a balance between niche differences stabilizing coexistence and fitness differences promoting competitive exclusion. Furthermore, coadaptation allowed prey and predator species to cluster into different functional groups. This equalized the fitness of similar species while maintaining sufficient niche differences among functionally different species delaying or preventing competitive exclusion. In contrast to pre-
vious studies, the emergent feedback between biomass and trait dynamics enabled supersaturated coexistence for a broad range of potential trait adaptation and parameters. We conclude that accounting for trait adaptation may explain stable and supersaturated species coexistence for a broad range of environmental conditions in natural systems when the absence of such adaptive changes would preclude it. Small trait changes, coincident with those that may occur within many natural populations, greatly enlarged the number of coexisting species.
Species can adjust their traits in response to selection which may strongly influence species coexistence. Nevertheless, current theory mainly assumes distinct and time-invariant trait values. We examined the combined effects of the range and the speed of trait adaptation on species coexistence using an innovative multispecies predator–prey model. It allows for temporal trait changes of all predator and prey species and thus simultaneous coadaptation within and among trophic levels. We show that very small or slow trait adaptation did not facilitate coexistence because the stabilizing niche differences were not sufficient to offset the fitness differences. In contrast, sufficiently large and fast trait adaptation jointly promoted stable or neutrally stable species coexistence. Continuous trait adjustments in response to selection enabled a temporally variable convergence and divergence of species traits; that is, species became temporally more similar (neutral theory) or dissimilar (niche theory) depending on the selection pressure, resulting over time in a balance between niche differences stabilizing coexistence and fitness differences promoting competitive exclusion. Furthermore, coadaptation allowed prey and predator species to cluster into different functional groups. This equalized the fitness of similar species while maintaining sufficient niche differences among functionally different species delaying or preventing competitive exclusion. In contrast to previous studies, the emergent feedback between biomass and trait dynamics enabled supersaturated coexistence for a broad range of potential trait adaptation and parameters. We conclude that accounting for trait adaptation may explain stable and supersaturated species coexistence for a broad range of environmental conditions in natural systems when the absence of such adaptive changes would preclude it. Small trait changes, coincident with those that may occur within many natural populations, greatly enlarged the number of coexisting species.
Species can adjust their traits in response to selection which may strongly influence species coexistence. Nevertheless, current theory mainly assumes distinct and time-invariant trait values. We examined the combined effects of the range and the speed of trait adaptation on species coexistence using an innovative multispecies predator-prey model. It allows for temporal trait changes of all predator and prey species and thus simultaneous coadaptation within and among trophic levels. We show that very small or slow trait adaptation did not facilitate coexistence because the stabilizing niche differences were not sufficient to offset the fitness differences. In contrast, sufficiently large and fast trait adaptation jointly promoted stable or neutrally stable species coexistence. Continuous trait adjustments in response to selection enabled a temporally variable convergence and divergence of species traits; that is, species became temporally more similar (neutral theory) or dissimilar (niche theory) depending on the selection pressure, resulting over time in a balance between niche differences stabilizing coexistence and fitness differences promoting competitive exclusion. Furthermore, coadaptation allowed prey and predator species to cluster into different functional groups. This equalized the fitness of similar species while maintaining sufficient niche differences among functionally different species delaying or preventing competitive exclusion. In contrast to previous studies, the emergent feedback between biomass and trait dynamics enabled supersaturated coexistence for a broad range of potential trait adaptation and parameters. We conclude that accounting for trait adaptation may explain stable and supersaturated species coexistence for a broad range of environmental conditions in natural systems when the absence of such adaptive changes would preclude it. Small trait changes, coincident with those that may occur within many natural populations, greatly enlarged the number of coexisting species.
Well-developed phonological awareness skills are a core prerequisite for early literacy development. Although effective phonological awareness training programs exist, children at risk often do not reach similar levels of phonological awareness after the intervention as children with normally developed skills. Based on theoretical considerations and first promising results the present study explores effects of an early musical training in combination with a conventional phonological training in children with weak phonological awareness skills. Using a quasi-experimental pretest-posttest control group design and measurements across a period of 2 years, we tested the effects of two interventions: a consecutive combination of a musical and a phonological training and a phonological training alone. The design made it possible to disentangle effects of the musical training alone as well the effects of its combination with the phonological training. The outcome measures of these groups were compared with the control group with multivariate analyses, controlling for a number of background variables. The sample included N = 424 German-speaking children aged 4–5 years at the beginning of the study. We found a positive relationship between musical abilities and phonological awareness. Yet, whereas the well-established phonological training produced the expected effects, adding a musical training did not contribute significantly to phonological awareness development. Training effects were partly dependent on the initial level of phonological awareness. Possible reasons for the lack of training effects in the musical part of the combination condition as well as practical implications for early literacy education are discussed.
Reconstructions of the deposition rate of windblown mineral dust in ocean sediments offer an important means of tracking past climate changes and of assessing the radiative and biogeochemical impacts of dust in past climates. Dust flux estimates in ocean sediments have commonly been based on the operationally defined lithogenic fraction of sediment samples. More recently, dust fluxes have been estimated from measurements of helium and thorium, as rare isotopes of these elements (He-3 and Th-230) allow estimates of sediment flux, and the dominant isotopes (He-4 and Th-232) are uniquely associated with the lithogenic fraction of marine sediments. In order to improve the fidelity of dust flux reconstructions based on He and Th, we present a survey of He and Th concentrations in sediments from dust source areas in East Asia, Australia and South America. Our data show systematic relationships between He and Th concentrations and grain size, with He concentrations decreasing and Th concentrations increasing with decreasing grain size. We find consistent He and Th concentrations in the fine fraction (<5 mu m) of samples from East Asia, Australia and Central South America (Puna-Central West Argentina), with Th concentrations averaging 14 mu g/g and He concentrations averaging 2 mu cc STP/g. We recommend use of these values for estimating dust fluxes in sediments where dust is dominantly fine-grained, and suggest that previous studies may have systematically overestimated Th-based dust fluxes by 30%. Source areas in Patagonia appear to have lower He and Th contents than other regions, as fine fraction concentrations average 0.8 mu cc STP/g and 9 mu g/g for He-4 and Th-232, respectively. The impact of grain size on lithogenic He and Th concentrations should be taken into account in sediments proximal to dust sources where dust grain size may vary considerably. Our data also have important implications for the hosts of He in long-traveled dust and for the He-3/He-4 ratio used for terrigenous He in studies of extraterrestrial He in sediments and ice. We also investigate the use of He/Th ratios as a provenance tracer. Our results suggest differences in fine fraction He/Th ratios between East Asia, Australia, central South America and Patagonia, with ratios showing a positive relationship with the geological age of source rocks. He/Th ratios may thus provide useful provenance information, for example allowing separation of Patagonian sources from Puna-Central West Argentina or Australian dust sources. He/Th ratios in open-ocean marine sediments are similar to ratios in the fine fraction of upwind dust source areas. He/Th ratios in mid-latitude South Atlantic sediments suggest that dust in this region primarily derives from the Puna-Central West Argentina region (23-32 degrees S) rather than Patagonia (>38 degrees S). In the equatorial Pacific, He/Th ratios are much lower than in extratropical Pacific sediments or potential source areas measured as a part of this study (East Asia, South America, Australia) for reasons that are at present unclear, complicating their use as provenance tracers in this region. (C) 2015 Elsevier Ltd. All rights reserved.
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.
When realizing a programming language as VM, implementing behavior as part of the VM, as primitive, usually results in reduced execution times. But supporting and developing primitive functions requires more effort than maintaining and using code in the hosted language since debugging is harder, and the turn-around times for VM parts are higher. Furthermore, source artifacts of primitive functions are seldom reused in new implementations of the same language. And if they are reused, the existing API usually is emulated, reducing the performance gains. Because of recent results in tracing dynamic compilation, the trade-off between performance and ease of implementation, reuse, and changeability might now be decided adversely.
In this work, we investigate the trade-offs when creating primitives, and in particular how large a difference remains between primitive and hosted function run times in VMs with tracing just-in-time compiler. To that end, we implemented the algorithmic primitive BitBlt three times for RSqueak/VM. RSqueak/VM is a Smalltalk VM utilizing the PyPy RPython toolchain. We compare primitive implementations in C, RPython, and Smalltalk, showing that due to the tracing just-in-time compiler, the performance gap has lessened by one magnitude to one magnitude.
Arsenosugars are water-soluble arsenic species predominant in marine algae and other seafood including mussels and oysters. They typically occur at levels ranging from 2 to 50 mg arsenic/kg dry weight. Most of the arsenosugars contain arsenic as a dimethylarsinoyl group (Me2As(O)-), commonly referred to as the oxo forms, but thio analogues have also been identified in marine organisms and as metabolic products of oxo-arsenosugars. So far, no data regarding toxicity and toxicokinetics of thio-arsenosugars are available. This in vitro-based study indicates that thio-dimethylarsenosugar-glycerol exerts neither pronounced cytotoxicity nor genotoxicity even though this arsenical was bioavailable to human hepatic (HepG2) and urothelial (UROtsa) cells. Experiments with the Caco-2 intestinal barrier model mimicking human absorption indicate for the thio-arsenosugar-glycerol higher intestinal bioavailability as compared to the oxo-arsenosugars. Nevertheless, absorption estimates were much lower in comparison to other arsenicals including arsenite and arsenic-containing hydrocarbons. Arsenic speciation in cell lysates revealed that HepG2 cells are able to metabolise the thio-arsenosugar-glycerol to some extent to dimethylarsinic acid (DMA). These first in vitro data cannot fully exclude risks to human health related to the presence of thio-arsenosugars in food. (C) 2016 Elsevier GmbH. All rights reserved.
Towards the assimilation of tree-ring-width records using ensemble Kalman filtering techniques
(2016)
This paper investigates the applicability of the Vaganov–Shashkin–Lite (VSL) forward model for tree-ring-width chronologies as observation operator within a proxy data assimilation (DA) setting. Based on the principle of limiting factors, VSL combines temperature and moisture time series in a nonlinear fashion to obtain simulated TRW chronologies. When used as observation operator, this modelling approach implies three compounding, challenging features: (1) time averaging, (2) “switching recording” of 2 variables and (3) bounded response windows leading to “thresholded response”. We generate pseudo-TRW observations from a chaotic 2-scale dynamical system, used as a cartoon of the atmosphere-land system, and attempt to assimilate them via ensemble Kalman filtering techniques. Results within our simplified setting reveal that VSL’s nonlinearities may lead to considerable loss of assimilation skill, as compared to the utilization of a time-averaged (TA) linear observation operator. In order to understand this undesired effect, we embed VSL’s formulation into the framework of fuzzy logic (FL) theory, which thereby exposes multiple representations of the principle of limiting factors. DA experiments employing three alternative growth rate functions disclose a strong link between the lack of smoothness of the growth rate function and the loss of optimality in the estimate of the TA state. Accordingly, VSL’s performance as observation operator can be enhanced by resorting to smoother FL representations of the principle of limiting factors. This finding fosters new interpretations of tree-ring-growth limitation processes.
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.
The article focuses on comparative complementisers in comparative clauses expressing inequality in various languages, with particular attention paid to their role as lexicalising negative polarity. I argue that the relevant property follows from degree semantics, in that the comparative subclause encodes the inequality of the degree expressed by a matrix clausal element and the one expressed by the comparative operator. Just like ordinary negation, this has to be encoded overtly; however, as it does not constitute an instance of genuine clausal negation, the property cannot be encoded by an operator, and hence must be realised on a functional head, which is either the complementiser or a separate polarity head.
In experiments investigating sentence processing, eye movement measures such as fixation durations and regression proportions while reading are commonly used to draw conclusions about processing difficulties. However, these measures are the result of an interaction of multiple cognitive levels and processing strategies and thus are only indirect indicators of processing difficulty. In order to properly interpret an eye movement response, one has to understand the underlying principles of adaptive processing such as trade-off mechanisms between reading speed and depth of comprehension that interact with task demands and individual differences. Therefore, it is necessary to establish explicit models of the respective mechanisms as well as their causal relationship with observable behavior. There are models of lexical processing and eye movement control on the one side and models on sentence parsing and memory processes on the other. However, no model so far combines both sides with explicitly defined linking assumptions.
In this thesis, a model is developed that integrates oculomotor control with a parsing mechanism and a theory of cue-based memory retrieval. On the basis of previous empirical findings and independently motivated principles, adaptive, resource-preserving mechanisms of underspecification are proposed both on the level of memory access and on the level of syntactic parsing. The thesis first investigates the model of cue-based retrieval in sentence comprehension of Lewis & Vasishth (2005) with a comprehensive literature review and computational modeling of retrieval interference in dependency processing. The results reveal a great variability in the data that is not explained by the theory. Therefore, two principles, 'distractor prominence' and 'cue confusion', are proposed as an extension to the theory, thus providing a more adequate description of systematic variance in empirical results as a consequence of experimental design, linguistic environment, and individual differences. In the remainder of the thesis, four interfaces between parsing and eye movement control are defined: Time Out, Reanalysis, Underspecification, and Subvocalization. By comparing computationally derived predictions with experimental results from the literature, it is investigated to what extent these four interfaces constitute an appropriate elementary set of assumptions for explaining specific eye movement patterns during sentence processing. Through simulations, it is shown how this system of in itself simple assumptions results in predictions of complex, adaptive behavior.
In conclusion, it is argued that, on all levels, the sentence comprehension mechanism seeks a balance between necessary processing effort and reading speed on the basis of experience, task demands, and resource limitations. Theories of linguistic processing therefore need to be explicitly defined and implemented, in particular with respect to linking assumptions between observable behavior and underlying cognitive processes. The comprehensive model developed here integrates multiple levels of sentence processing that hitherto have only been studied in isolation. The model is made publicly available as an expandable framework for future studies of the interactions between parsing, memory access, and eye movement control.
As the world cannot be adequately understood from the vantage point of a single language, the literatures of the world can no longer be trimmed to a single world literature in the Goethean sense. This recognition bodes well for the future of philology and of literary production. Through multiperspectival writing, knowledge of life may be attainable without being reduced to a single political, medial, cartographical, geocultural, or aesthetic logic. As a laboratory for polylogical thinking, literature does not represent reality, as Erich Auerbach put it. Rather, it represents multiple lived, experienced, or relivable realities. Whoever is open to a polylogical reception of the literatures of the world can perceive and experience how life knowledge transforms into lived knowledge and how knowledge for survival turns into knowledge for living together. However, literature can be more than it is only if it stays aware of the void, of lack, of privation, of the interminable: aware of the end that never is an end. Such a planetary concept of the literatures of the world offers valuable opportunities to all those who do not fall into the trap of contenting themselves with a supposed abundance of text.
Touring Katutura!
(2016)
Guided sightseeing tours of the former township of Katutura have been offered in Windhoek since the mid-1990s. City tourism in the Namibian capital had thus become, at quite an early point in time, part of the trend towards utilising poor urban areas for purposes of tourism – a trend that set in at the beginning of the same decade. Frequently referred to as “slum tourism” or “poverty tourism”, the phenomenon of guided tours around places of poverty has not only been causing some media sensation and much public outrage since its emergence; in the past few years, it has developed into a vital field of scientific research, too. “Global Slumming” provides the grounds for a rethinking of the relationship between poverty and tourism in world society.
This book is the outcome of a study project of the Institute of Geography at the School of Cultural Studies and Social Science of the University of Osnabrueck, Germany. It represents the first empirical case study on township tourism in Namibia. It focuses on four aspects:
1. Emergence, development and (market) structure of township tourism in Windhoek
2. Expectations/imaginations, representations as well as perceptions of the township and its inhabitants from the tourist’s perspective
3. Perception and assessment of township tourism from the residents’ perspective
4. Local economic effects and the poverty-alleviating impact of township tourism
The aim is to make an empirical contribution to the discussion around the tourism-poverty nexus and to an understanding of the global phenomenon of urban poverty tourism.
Total protein concentration (TPC) is a key parameter in many biochemical experiments and its quantification is often necessary for isolation, separation, and analysis of proteins. A sensitive and rapid nanobead-based TPC quantification assay based on Forster Resonance Energy Transfer (FRET) has been developed. A new, highly luminescent Tb(III) complex has been synthesised and applied as donor in this FRET assay with an organic dye (Cy5) as acceptor. FRET-induced changes in luminescence have been investigated both at donor and acceptor emission wavelength using time-resolved luminescence spectroscopy with time-gated detection. In the assay, the Tb(III) complex and fine-tuned polyglycidyl methacrylate (PGMA) nanobeads ensure that an improvement in sensitivity and background reduction is achieved. Using 40 nm large PGMA nanobeads loaded with the Tb(III) complex, it is possible to determine TPC down to 50 ng mL(-1) in just 10 minutes. Through specific assay components the sensitivity has been improved when compared to existing nanobead-based assays and to currently known commercial methods. Additionally, the assay is relatively insensitive to the presence of contaminants, such as non-ionic detergents commonly found in biological samples. Due to no need for any centrifugal steps, this mix-and-measure bioassay can easily be implemented into routine TPC quantification protocols in biochemical laboratories.
This study presents new insights into null subjects, topic drop and the interpretation of topic-dropped elements. Besides providing an empirical data survey, it offers explanations to well-known problems, e.g. syncretisms in the context of null-subject licensing or the marginality of dropping an element which carries oblique case. The book constitutes a valuable source for both empirically and theoretically interested (generative) linguists.
To turn or not to turn?
(2016)
Bacteria typically swim in straight runs, interruped by sudden turning events. In particular, some species are limited to a reversal in the swimming direction as the only turning maneuver at their disposal. In a recent article, Grossmann et al (2016 New J. Phys. 18 043009) introduce a theoretical framework to analyze the diffusive properties of active particles following this type of run-and-reverse pattern. Based on a stochastic clock model to mimic the regulatory pathway that triggers reversal events, they show that a run-and-reverse swimmer can optimize its diffusive spreading by tuning the reversal rate according to the level of rotational noise. With their approach, they open up promising new perspectives of how to incorporate the dynamics of intracellular signaling into coarse-grained active particle descriptions.
Forecasting the onset and withdrawal of the Indian summer monsoon is crucial for the life and prosperity of more than one billion inhabitants of the Indian subcontinent. However, accurate prediction of monsoon timing remains a challenge, despite numerous efforts. Here we present a method for prediction of monsoon timing based on a critical transition precursor. We identify geographic regions-tipping elements of the monsoon-and use them as observation locations for predicting onset and withdrawal dates. Unlike most predictability methods, our approach does not rely on precipitation analysis but on air temperature and relative humidity, which are well represented both in models and observations. The proposed method allows to predict onset 2 weeks earlier and withdrawal dates 1.5 months earlier than existing methods. In addition, it enables to correctly forecast monsoon duration for some anomalous years, often associated with El Nino-Southern Oscillation.
We contribute to the theoretical understanding of randomized search heuristics by investigating their optimization behavior on satisfiable random k-satisfiability instances both in the planted solution model and the uniform model conditional on satisfiability. Denoting the number of variables by n, our main technical result is that the simple () evolutionary algorithm with high probability finds a satisfying assignment in time when the clause-variable density is at least logarithmic. For low density instances, evolutionary algorithms seem to be less effective, and all we can show is a subexponential upper bound on the runtime for densities below . We complement these mathematical results with numerical experiments on a broader density spectrum. They indicate that, indeed, the () EA is less efficient on lower densities. Our experiments also suggest that the implicit constants hidden in our main runtime guarantee are low. Our main result extends and considerably improves the result obtained by Sutton and Neumann (Lect Notes Comput Sci 8672:942-951, 2014) in terms of runtime, minimum density, and clause length. These improvements are made possible by establishing a close fitness-distance correlation in certain parts of the search space. This approach might be of independent interest and could be useful for other average-case analyses of randomized search heuristics. While the notion of a fitness-distance correlation has been around for a long time, to the best of our knowledge, this is the first time that fitness-distance correlation is explicitly used to rigorously prove a performance statement for an evolutionary algorithm.
Two experiments examined how individuals respond to a restriction presented within an approach versus an avoidance frame. In Study 1, working on a problem-solving task, participants were initially free to choose their strategy, but for a second task were told to change their strategy. The message to change was embedded in either an approach or avoidance frame. When confronted with an avoidance compared to an approach frame, the participants’ reactance toward the request was greater and, in turn, led to impaired performance. The role of reactance as a response to threat to freedom was explicitly examined in Study 2, in which participants evaluated a potential change in policy affecting their program of study herein explicitly varying whether a restriction was present or absent and whether the message was embedded in an approach versus avoidance frame. When communicated with an avoidance frame and as a restriction, participants showed the highest resistance in terms of reactance, message agreement and evaluation of the communicator. The difference in agreement with the change was mediated by reactance only when a restriction was present. Overall, avoidance goal frames were associated with more resistance to change on different levels of experience (reactance, performance, and person perception). Reactance mediated the effect of goal frame on other outcomes only when a restriction was present.
Two experiments examined how individuals respond to a restriction presented within an approach versus an avoidance frame. In Study 1, working on a problem-solving task, participants were initially free to choose their strategy, but for a second task were told to change their strategy. The message to change was embedded in either an approach or avoidance frame. When confronted with an avoidance compared to an approach frame, the participants’ reactance toward the request was greater and, in turn, led to impaired performance. The role of reactance as a response to threat to freedom was explicitly examined in Study 2, in which participants evaluated a potential change in policy affecting their program of study herein explicitly varying whether a restriction was present or absent and whether the message was embedded in an approach versus avoidance frame. When communicated with an avoidance frame and as a restriction, participants showed the highest resistance in terms of reactance, message agreement and evaluation of the communicator. The difference in agreement with the change was mediated by reactance only when a restriction was present. Overall, avoidance goal frames were associated with more resistance to change on different levels of experience (reactance, performance, and person perception). Reactance mediated the effect of goal frame on other outcomes only when a restriction was present.
Two experiments examined how individuals respond to a restriction presented within an approach versus an avoidance frame. In Study 1, working on a problem-solving task, participants were initially free to choose their strategy, but for a second task were told to change their strategy. The message to change was embedded in either an approach or avoidance frame. When confronted with an avoidance compared to an approach frame, the participants’ reactance toward the request was greater and, in turn, led to impaired performance. The role of reactance as a response to threat to freedom was explicitly examined in Study 2, in which participants evaluated a potential change in policy affecting their program of study herein explicitly varying whether a restriction was present or absent and whether the message was embedded in an approach versus avoidance frame. When communicated with an avoidance frame and as a restriction, participants showed the highest resistance in terms of reactance, message agreement and evaluation of the communicator. The difference in agreement with the change was mediated by reactance only when a restriction was present. Overall, avoidance goal frames were associated with more resistance to change on different levels of experience (reactance, performance, and person perception). Reactance mediated the effect of goal frame on other outcomes only when a restriction was present.
Theses
(2016)
Responsive inverse opal hydrogels functionalized by boroxole moieties were synthesized and explored as sensor platforms for various low molar mass as well as polymeric diols and polyols, including saccharides, glycopolymers and catechols, by exploiting the diol induced modulation of their structural color. The underlying thermoresponsive water-soluble copolymers and hydrogels exhibit a coil-to-globule or volume phase transition, respectively, of the LCST-type. They were prepared from oligoethylene oxide methacrylate (macro)monomers and functionalized via copolymerization to bear benzoboroxole moieties. The resulting copolymers represent weak polyacids, which can bind specifically to diols within an appropriate pH window. Due to the resulting modulation of the overall hydrophilicity of the systems and the consequent shift of their phase transition temperature, the usefulness of such systems for indicating the presence of catechols, saccharides, and glycopolymers was studied, exploiting the diol/polyol induced shifts of the soluble polymers’ cloud point, or the induced changes of the hydrogels’ swelling. In particular, the increased acidity of benzoboroxoles compared to standard phenylboronic acids allowed performing the studies in PBS buffer (phosphate buffered saline) at the physiologically relevant pH of 7.4. The inverse opals constructed of these thermo- and analyte-responsive hydrogels enabled following the binding of specific diols by the induced shift of the optical stop band. Their highly porous structure enabled the facile and specific optical detection of not only low molar mass but also of high molar mass diol/polyol analytes such as glycopolymers. Accordingly, such thermoresponsive inverse opal systems functionalized with recognition units represent attractive and promising platforms for the facile sensing of even rather big analytes by simple optical means, or even by the bare eye.
The authors report on the fabrication of a thermoresponsive biosensor for the amperometric detection of glucose. Screen printed electrodes with heatable gold working electrodes were modified by a thermoresponsive statistical copolymer [polymer I: poly(omega-ethoxytriethylenglycol methacrylate-omega-3-(N,N-dimethyl-N-2-methacryloyloxyethyl ammonio) propanesulfonate-co-omega-butoxydiethylenglycol methacrylate-co-2-(4-benzoyl-phenoxy)ethyl methacrylate)] with a lower critical solution temperature of around 28 degrees C in aqueous solution via electrochemically induced codeposition with a pH-responsive redox-polymer [polymer II: poly(glycidyl methacrylate-co-allyl methacrylate-co-poly(ethylene glycol) methacrylate-co-butyl acrylate-co-2-(dimethylamino) ethyl methacrylate)-[Os(bpy)(2)(4-(((2-(2-(2-aminoethoxy) ethoxy) ethyl) amino) methyl)-N,N-dimethylpicolinamide)](2+)] and pyrroloquinoline quinone-soluble glucose dehydrogenase acting as biological recognition element. Polymer II bears covalently bound Os-complexes that act as redox mediators for shuttling electrons between the enzyme and the electrode surface. Polymer I acts as a temperature triggered immobilization matrix. Probing the catalytic current as a function of the working electrode temperature shows that the activity of the biosensor is dramatically reduced above the phase transition temperature of polymer I. Thus, the local modulation of the temperature at the interphase between the electrode and the bioactive layer allows switching the biosensor from an on-to an off-state without heating of the surrounding analyte solution. (C) 2015 American Vacuum Society.
A series of hydrophobically end-capped linear triblock copolymers as well as of three-arm and four-arm star block copolymers was synthesized in a one-pot procedure from N,N-dimethylacrylamide (DMA) and N, N-diethylacrylamide (DEA). The sequential reversible addition-fragmentation chain transfer (RAFT) polymerization of these monomers via the R-approach using bi-, tri- and tetrafunctional chain transfer agents (CrAs) bearing hydrophobic dodecyl moieties proceeded in a well-controlled manner up to almost quantitative conversion. Polymers with molar masses up to 150 kDa, narrow molar mass distribution (PDI <= 1.3) and high end group functionality were obtained, which are thermoresponsive in aqueous solution showing a LCST (lower critical solution temperature) transition. The temperature-dependent associative behavior of the polymers was examined using turbidimetry, static and dynamic light scattering (SLS, DLS), and small angle neutron scattering (SANS) for structural analysis. At 25 degrees C, the polymers form weak transient networks, and rather small hydrophobic domains are already present for polymer concentrations of 5 wt%. However, when heating above the LCST transition (35-40 degrees C) of the PDEA blocks, the enhanced formation of hydrophobic domains is observed by means of light and neutron scattering. These domains have a size of about 12-15 nm and must be effectively physically cross-linked as they induce high viscosity for the more concentrated samples. SANS shows that these domains are ordered as evidenced by the appearance of a correlation peak. The copolymer architecture affects in particular the extent of ordering as the four-arm star block copolymer shows much more repulsive interactions compared to the analogous copolymers with a lower number of arms. (C) 2016 Elsevier Ltd. All rights reserved.
Thermophony in real gases
(2016)
A thermophone is an electrical device for sound generation. The advantages of thermophones over conventional sound transducers such as electromagnetic, electrostatic or piezoelectric transducers are their operational principle which does not require any moving parts, their resonance-free behavior, their simple construction and their low production costs.
In this PhD thesis, a novel theoretical model of thermophonic sound generation in real gases has been developed. The model is experimentally validated in a frequency range from 2 kHz to 1 MHz by testing more then fifty thermophones of different materials, including Carbon nano-wires, Titanium, Indium-Tin-Oxide, different sizes and shapes for sound generation in gases such as air, argon, helium, oxygen, nitrogen and sulfur hexafluoride.
Unlike previous approaches, the presented model can be applied to different kinds of thermophones and various gases, taking into account the thermodynamic properties of thermophone materials and of adjacent gases, degrees of freedom and the volume occupied by the gas atoms and molecules, as well as sound attenuation effects, the shape and size of the thermophone surface and the reduction of the generated acoustic power due to photonic emission. As a result, the model features better prediction accuracy than the existing models by a factor up to 100. Moreover, the new model explains previous experimental findings on thermophones which can not be explained with the existing models.
The acoustic properties of the thermophones have been tested in several gases using unique, highly precise experimental setups comprising a Laser-Doppler-Vibrometer combined with a thin polyethylene film which acts as a broadband and resonance-free sound-pressure detector. Several outstanding properties of the thermophones have been demonstrated for the first time, including the ability to generate arbitrarily shaped acoustic signals, a greater acoustic efficiency compared to conventional piezoelectric and electrostatic airborne ultrasound transducers, and applicability as powerful and tunable sound sources with a bandwidth up to the megahertz range and beyond.
Additionally, new applications of thermophones such as the study of physical properties of gases, the thermo-acoustic gas spectroscopy, broad-band characterization of transfer functions of sound and ultrasound detection systems, and applications in non-destructive materials testing are discussed and experimentally demonstrated.
Widespread landscape changes are presently observed in the Arctic and are most likely to
accelerate in the future, in particular in permafrost regions which are sensitive to climate warming. To assess current and future developments, it is crucial to understand past
environmental dynamics in these landscapes. Causes and interactions of environmental variability can hardly be resolved by instrumental records covering modern time scales. However, long-term
environmental variability is recorded in paleoenvironmental archives. Lake sediments are important archives that allow reconstruction of local limnogeological processes as well as past environmental changes driven directly or indirectly by climate dynamics. This study aims at
reconstructing Late Quaternary permafrost and thermokarst dynamics in central-eastern Beringia,
the terrestrial land mass connecting Eurasia and North America during glacial sea-level low stands. In order to investigate development, processes and influence of thermokarst dynamics, several sediment cores from extant lakes and drained lake basins were analyzed to answer the
following research questions:
1. When did permafrost degradation and thermokarst lake development take place and what were enhancing and inhibiting environmental factors?
2. What are the dominant processes during thermokarst lake development and how are
they reflected in proxy records?
3. How did, and still do, thermokarst dynamics contribute to the inventory and properties of organic matter in sediments and the carbon cycle?
Methods applied in this study are based upon a multi-proxy approach combining
sedimentological, geochemical, geochronological, and micropaleontological analyses, as well as
analyses of stable isotopes and hydrochemistry of pore-water and ice. Modern field observations of water quality and basin morphometrics complete the environmental investigations.
The investigated sediment cores reveal permafrost degradation and thermokarst dynamics on different time scales. The analysis of a sediment core from GG basin on the northern Seward
Peninsula (Alaska) shows prevalent terrestrial accumulation of yedoma throughout the Early to
Mid Wisconsin with intermediate wet conditions at around 44.5 to 41.5 ka BP. This first wetland
development was terminated by the accumulation of a 1-meter-thick airfall tephra most likely originating from the South Killeak Maar eruption at 42 ka BP. A depositional hiatus between 22.5 and 0.23 ka BP may indicate thermokarst lake formation in the surrounding of the site which forms a yedoma upland till today. The thermokarst lake forming GG basin initiated 230 ± 30 cal a
BP and drained in Spring 2005 AD. Four years after drainage the lake talik was still unfrozen below 268 cm depth.
A permafrost core from Mama Rhonda basin on the northern Seward Peninsula preserved a
full lacustrine record including several lake phases. The first lake generation developed at 11.8 cal ka BP during the Lateglacial-Early Holocene transition; its old basin (Grandma Rhonda) is still partially preserved at the southern margin of the study basin. Around 9.0 cal ka BP a shallow and more dynamic thermokarst lake developed with actively eroding shorelines and potentially intermediate shallow water or wetland phases (Mama Rhonda). Mama Rhonda lake drainage at 1.1 cal ka BP was followed by gradual accumulation of terrestrial peat and top-down refreezing of the lake talik. A significant lower organic carbon content was measured in Grandma Rhonda deposits (mean TOC of 2.5 wt%) than in Mama Rhonda deposits (mean TOC of 7.9 wt%) highlighting the impact of thermokarst dynamics on biogeochemical cycling in different lake generations by thawing and mobilization of organic carbon into the lake system.
Proximal and distal sediment cores from Peatball Lake on the Arctic Coastal Plain of Alaska revealed young thermokarst dynamics since about 1,400 years along a depositional gradient based on reconstructions from shoreline expansion rates and absolute dating results. After its initiation as a remnant pond of a previous drained lake basin, a rapidly deepening lake with increasing oxygenation of the water column is evident from laminated sediments, and higher Fe/Ti and Fe/S ratios in the sediment. The sediment record archived characterizing shifts in depositional regimes and sediment sources from upland deposits and re-deposited sediments from drained thaw lake basins depending on the gradually changing shoreline configuration. These changes are evident from alternating organic inputs into the lake system which highlights the potential for thermokarst lakes to recycle old carbon from degrading permafrost deposits of its catchment.
The lake sediment record from Herschel Island in the Yukon (Canada) covers the full Holocene period. After its initiation as a thermokarst lake at 11.7 cal ka BP and intense thermokarst activity until 10.0 cal ka BP, the steady sedimentation was interrupted by a depositional hiatus at 1.6 cal ka BP which likely resulted from lake drainage or allochthonous slumping due to collapsing shore lines. The specific setting of the lake on a push moraine composed of marine deposits is reflected in the sedimentary record. Freshening of the maturing lake is indicated by decreasing electrical conductivity in pore-water. Alternation of marine to freshwater ostracods and foraminifera confirms decreasing salinity as well but also reflects episodical re-deposition of allochthonous marine sediments.
Based on permafrost and lacustrine sediment records, this thesis shows examples of the Late Quaternary evolution of typical Arctic permafrost landscapes in central-eastern Beringia and the complex interaction of local disturbance processes, regional environmental dynamics and global climate patterns. This study confirms that thermokarst lakes are important agents of organic matter recycling in complex and continuously changing landscapes.
Quantitative thermodynamic and geochemical modeling is today applied in a variety of geological environments from the petrogenesis of igneous rocks to the oceanic realm. Thermodynamic calculations are used, for example, to get better insight into lithosphere dynamics, to constrain melting processes in crust and mantle as well as to study fluid-rock interaction. The development of thermodynamic databases and computer programs to calculate equilibrium phase diagrams have greatly advanced our ability to model geodynamic processes from subduction to orogenesis. However, a well-known problem is that despite its broad application the use and interpretation of thermodynamic models applied to natural rocks is far from straightforward. For example, chemical disequilibrium and/or unknown rock properties, such as fluid activities, complicate the application of equilibrium thermodynamics.
One major aspect of the publications presented in this Habilitationsschrift are new approaches to unravel dynamic and chemical histories of rocks that include applications to chemically open system behaviour. This approach is especially important in rocks that are affected by element fractionation due to fractional crystallisation and fluid loss during dehydration reactions. Furthermore, chemically open system behaviour has also to be considered for studying fluid-rock interaction processes and for extracting information from compositionally zoned metamorphic minerals. In this Habilitationsschrift several publications are presented where I incorporate such open system behaviour in the forward models by incrementing the calculations and considering changing reacting rock compositions during metamorphism. I apply thermodynamic forward modelling incorporating the effects of element fractionation in a variety of geodynamic and geochemical applications in order to better understand lithosphere dynamics and mass transfer in solid rocks.
In three of the presented publications I combine thermodynamic forward models with trace element calculations in order to enlarge the application of geochemical numerical forward modeling. In these publications a combination of thermodynamic and trace element forward modeling is used to study and quantify processes in metamorphic petrology at spatial scales from µm to km. In the thermodynamic forward models I utilize Gibbs energy minimization to quantify mineralogical changes along a reaction path of a chemically open fluid/rock system. These results are combined with mass balanced trace element calculations to determine the trace element distribution between rock and melt/fluid during the metamorphic evolution. Thus, effects of mineral reactions, fluid-rock interaction and element transport in metamorphic rocks on the trace element and isotopic composition of minerals, rocks and percolating fluids or melts can be predicted.
One of the included publications shows that trace element growth zonations in metamorphic garnet porphyroblasts can be used to get crucial information about the reaction path of the investigated sample. In order to interpret the major and trace element distribution and zoning patterns in terms of the reaction history of the samples, we combined thermodynamic forward models with mass-balance rare earth element calculations. Such combined thermodynamic and mass-balance calculations of the rare earth element distribution among the modelled stable phases yielded characteristic zonation patterns in garnet that closely resemble those in the natural samples. We can show in that paper that garnet growth and trace element incorporation occurred in near thermodynamic equilibrium with matrix phases during subduction and that the rare earth element patterns in garnet exhibit distinct enrichment zones that fingerprint the minerals involved in the garnet-forming reactions.
In two of the presented publications I illustrate the capacities of combined thermodynamic-geochemical modeling based on examples relevant to mass transfer in subduction zones. The first example focuses on fluid-rock interaction in and around a blueschist-facies shear zone in felsic gneisses, where fluid-induced mineral reactions and their effects on boron (B) concentrations and isotopic compositions in white mica are modeled. In the second example, fluid release from a subducted slab and associated transport of B and variations in B concentrations and isotopic compositions in liberated fluids and residual rocks are modeled. I show that, combined with experimental data on elemental partitioning and isotopic fractionation, thermodynamic forward modeling unfolds enormous capacities that are far from exhausted.
In my publications presented in this Habilitationsschrift I compare the modeled results to geochemical data of natural minerals and rocks and demonstrate that the combination of thermodynamic and geochemical models enables quantification of metamorphic processes and insights into element cycling that would have been unattainable so far.
Thus, the contributions to the science community presented in this Habilitatonsschrift concern the fields of petrology, geochemistry, geochronology but also ore geology that all use thermodynamic and geochemical models to solve various problems related to geo-materials.