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The photosynthetic carbon metabolism, including the Calvin-Benson cycle, is the primary pathway in C-3-plants, producing starch and sucrose from CO2. Understanding the interplay between regulation and efficiency of this pathway requires the development of mathematical models which would explain the observed dynamics of metabolic transformations. Here, we address this question by casting the existing models of Calvin-Benson cycle and the end-product processes into an analysis framework which not only facilitates the comparison of the different models, but also allows for their ranking with respect to chosen criteria, including stability, sensitivity, robustness and/or compliance with experimental data. The importance of the photosynthetic carbon metabolism for the increase of plant biomass has resulted in many models with various levels of detail. We provide the largest compendium of 15 existing, well-investigated models together with a comprehensive classification as well as a ranking framework to determine the best-performing models for metabolic engineering and planning of in silica experiments. The classification can be additionally used, based on the model structure, as a tool to identify the models which match best the experimental design. The provided ranking is just one alternative to score models and, by changing the weighting factor, this framework also could be applied for selection of other criteria of interest.
Giant planets helped to shape the conditions we see in the Solar System today and they account for more than 99% of the mass of the Sun's planetary system. They can be subdivided into the Ice Giants (Uranus and Neptune) and the Gas Giants (Jupiter and Saturn), which differ from each other in a number of fundamental ways. Uranus, in particular is the most challenging to our understanding of planetary formation and evolution, with its large obliquity, low self-luminosity, highly asymmetrical internal field, and puzzling internal structure. Uranus also has a rich planetary system consisting of a system of inner natural satellites and complex ring system, five major natural icy satellites, a system of irregular moons with varied dynamical histories, and a highly asymmetrical magnetosphere. Voyager 2 is the only spacecraft to have explored Uranus, with a flyby in 1986, and no mission is currently planned to this enigmatic system. However, a mission to the uranian system would open a new window on the origin and evolution of the Solar System and would provide crucial information on a wide variety of physicochemical processes in our Solar System. These have clear implications for understanding exoplanetary systems. In this paper we describe the science case for an orbital mission to Uranus with an atmospheric entry probe to sample the composition and atmospheric physics in Uranus' atmosphere. The characteristics of such an orbiter and a strawman scientific payload are described and we discuss the technical challenges for such a mission. This paper is based on a white paper submitted to the European Space Agency's call for science themes for its large-class mission programme in 2013.
The stem bark extract of Schizozygia coffaeoides (Apocynaceae) showed moderate antiplasmodial activity (IC50 = 8-12 mu g/mL) against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) strains of Plasmodium falciparum. Chromatographic separation of the extract led to the isolation of a new schizozygane indoline alkaloid, named 3-oxo-14 alpha, 15 alpha-epoxyschizozygine. In addition, two dimeric anthraquinones, cassiamin A and cassiamin B, were identified for the first time in the family Apocynaceae. The structures of the isolated compounds were deduced on the basis of spectroscopic evidence. The schizozygane indole alkaloids showed good to moderate antiplasmodial activities (IC50 = 13-52 mu m). (C) 2014 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.
Dissolved organic carbon (DOC) concentrations - mainly of terrestrial origin - are increasing worldwide in inland waters. Heterotrophic bacteria are the main consumers of DOC and thus determine DOC temporal dynamics and availability for higher trophic levels. Our aim was to study bacterial carbon (C) turnover with respect to DOC quantity and chemical quality using both allochthonous and autochthonous DOC sources. We incubated a natural bacterial community with allochthonous C (C-13-labeled beech leachate) and increased concentrations and pulses (intermittent occurrence of organic matter input) of autochthonous C (phytoplankton lysate). We then determined bacterial C consumption, activities, and community composition together with the C flow through bacteria using stable C isotopes. The chemical analysis of single sources revealed differences in aromaticity and low-and high-molecular-weight substance fractions (LMWS and HMWS, respectively) between allochthonous and autochthonous C sources. Both DOC sources (allochthonous and autochthonous DOC) were metabolized at a high bacterial growth efficiency (BGE) around 50%. In treatments with mixed sources, rising concentrations of added autochthonous DOC resulted in a further, significant increase in bacterial DOC consumption of up to 68% when nutrients were not limiting. This rise was accompanied by a decrease in the humic substance (HS) fraction and an increase in bacterial biomass. Changes in DOC concentration and consumption in mixed treatments did not affect bacterial community composition (BCC), but BCC differed in single vs. mixed incubations. Our study highlights that DOC quantity affects bacterial C consumption but not BCC in nutrient-rich aquatic systems. BCC shifted when a mixture of allochthonous and autochthonous C was provided simultaneously to the bacterial community. Our results indicate that chemical quality rather than source of DOC per se (allochthonous vs. autochthonous) determines bacterial DOC turnover.
Confusion about model validation is one of the main challenges in using ecological models for decision support, such as the regulation of pesticides. Decision makers need to know whether a model is a sufficiently good representation of its real counterpart and what criteria can be used to answer this question. Unclear terminology is one of the main obstacles to a good understanding of what model validation is, how it works, and what it can deliver. Therefore, we performed a literature review and derived a standard set of terms. 'Validation' was identified as a catch-all term, which is thus useless for any practical purpose. We introduce the term 'evaludation', a fusion of 'evaluation' and 'validation', to describe the entire process of assessing a model's quality and reliability. Considering the iterative nature of model development, the modelling cycle, we identified six essential elements of evaludation: (i) 'data evaluation' for scrutinising the quality of numerical and qualitative data used for model development and testing; (ii) 'conceptual model evaluation' for examining the simplifying assumptions underlying a model's design; (iii) 'implementation verification' for testing the model's implementation in equations and as a computer programme; (iv) 'model output verification' for comparing model output to data and patterns that guided model design and were possibly used for calibration; (v) 'model analysis' for exploring the model's sensitivity to changes in parameters and process formulations to make sure that the mechanistic basis of main behaviours of the model has been well understood; and (vi) 'model output corroboration' for comparing model output to new data and patterns that were not used for model development and parameterisation. Currently, most decision makers require 'validating' a model by testing its predictions with new experiments or data. Despite being desirable, this is neither sufficient nor necessary for a model to be useful for decision support. We believe that the proposed set of terms and its relation to the modelling cycle can help to make quality assessments and reality checks of ecological models more comprehensive and transparent. (C) 2013 Elsevier B.V. All rights reserved.
There is robust evidence showing a link between executive function (EF) and theory of mind (ToM) in 3-to 5-year-olds. However, it is unclear whether this relationship extends to middle childhood. In addition, there has been much discussion about the nature of this relationship. Whereas some authors claim that ToM is needed for EF, others argue that ToM requires EF. To date, however, studies examining the longitudinal relationship between distinct sub components of EF [i.e., attention shifting, working memory (WM) updating, inhibition] and ToM in middle childhood are rare. The present study examined (1) the relationship between three EF subcomponents (attention shifting, WM updating, inhibition) and ToM in middle childhood, and (2) the longitudinal reciprocal relationships between the EF subcomponents and ToM across a 1-year period. EF and ToM measures were assessed experimentally in a sample of 1,657 children (aged 6-11 years) at time point one (t1) and 1 year later at time point two (t2). Results showed that the concurrent relationships between all three EF subcomponents and ToM pertained in middle childhood at t1 and t2, respectively, even when age, gender, and fluid intelligence were partialle dout. Moreover, cross-lagged structural equation modeling (again, controlling for age, gender, and fluid intelligence, as well as for the earlier levels of the target variables), revealed partial support for the view that early ToM predictslater EF, but stronger evidence for the assumption that early EF predictslater ToM. The latter was found for attention shifting and WM updating, but not for inhibition. This reveals the importance of studying the exact interplay of ToM and EF across childhood development, especially with regard to different EF subcomponents. Most likely, understanding others' mental states at different levels of perspective-taking requires specific EF subcomponents, suggesting developmental change in the relations between EF and ToM across childhood.
This paper examines cyclical changes in comparative subclauses, showing how operators are reanalysed as complementisers via the general mechanism of the relative cycle, and how this is related to whether certain lexical elements have to be deleted at the left periphery. I also show that only operators appearing without a lexical XP can be grammaticalised, which follows from the nature of the formal features associated with the various operator elements. Though the main focus is on Hungarian historical data, the framework can be applied to other languages too, such as German and Italian, since the changes stem from general principles of economy.
The paper argues that structural case assignment properties of English and German reduced comparative subclauses arise from syntactic requirements as well as processes holding at the syntax-phonology interface. I show that constructions involving both an adjectival and a verbal predicate require the subject remnant of the adjectival predicate to be marked for the accusative case both in English and German, which cannot be explained by the notion of default accusative case, especially because German has no default accusative case. I argue that a phonologically defective subclause is reanalysed as part of the matrix clausal object, and hence receives accusative morphological case.
Adopting a minimalist framework, the dissertation provides an analysis for the syntactic structure of comparatives, with special attention paid to the derivation of the subclause. The proposed account explains how the comparative subclause is connected to the matrix clause, how the subclause is formed in the syntax and what additional processes contribute to its final structure. In addition, it casts light upon these problems in cross-linguistic terms and provides a model that allows for synchronic and diachronic differences. This also enables one to give a more adequate explanation for the phenomena found in English comparatives since the properties of English structures can then be linked to general settings of the language and hence need no longer be considered as idiosyncratic features of the grammar of English. First, the dissertation provides a unified analysis of degree expressions, relating the structure of comparatives to that of other degrees. It is shown that gradable adjectives are located within a degree phrase (DegP), which in turn projects a quantifier phrase (QP) and that these two functional layers are always present, irrespectively of whether there is a phonologically visible element in these layers. Second, the dissertation presents a novel analysis of Comparative Deletion by reducing it to an overtness constraint holding on operators: in this way, it is reduced to morphological differences and cross-linguistic variation is not conditioned by way of postulating an arbitrary parameter. Cross-linguistic differences are ultimately dependent on whether a language has overt operators equipped with the relevant – [+compr] and [+rel] – features. Third, the dissertation provides an adequate explanation for the phenomenon of Attributive Comparative Deletion, as attested in English, by way of relating it to the regular mechanism of Comparative Deletion. I assume that Attributive Comparative Deletion is not a universal phenomenon, and its presence in English can be conditioned by independent, more general rules, while the absence of such restrictions leads to its absence in other languages. Fourth, the dissertation accounts for certain phenomena related to diachronic changes, examining how the changes in the status of comparative operators led to changes in whether Comparative Deletion is attested in a given language: I argue that only operators without a lexical XP can be grammaticalised. The underlying mechanisms underlying are essentially general economy principles and hence the processes are not language-specific or exceptional. Fifth, the dissertation accounts for optional ellipsis processes that play a crucial role in the derivation of typical comparative subclauses. These processes are not directly related to the structure of degree expressions and hence the elimination of the quantified expression from the subclause; nevertheless, they are shown to be in interaction with the mechanisms underlying Comparative Deletion or the absence thereof.
Biosensors for the detection of benzaldehyde and g-aminobutyric acid (GABA) are reported using aldehyde oxidoreductase PaoABC from Escherichia coli immobilized in a polymer containing bound low potential osmium redox complexes. The electrically connected enzyme already electrooxidizes benzaldehyde at potentials below −0.15 V (vs. Ag|AgCl, 1 M KCl). The pH-dependence of benzaldehyde oxidation can be strongly influenced by the ionic strength. The effect is similar with the soluble osmium redox complex and therefore indicates a clear electrostatic effect on the bioelectrocatalytic efficiency of PaoABC in the osmium containing redox polymer. At lower ionic strength, the pH-optimum is high and can be switched to low pH-values at high ionic strength. This offers biosensing at high and low pH-values. A “reagentless” biosensor has been formed with enzyme wired onto a screen-printed electrode in a flow cell device. The response time to addition of benzaldehyde is 30 s, and the measuring range is between 10–150 µM and the detection limit of 5 µM (signal to noise ratio 3:1) of benzaldehyde. The relative standard deviation in a series (n = 13) for 200 µM benzaldehyde is 1.9%. For the biosensor, a response to succinic semialdehyde was also identified. Based on this response and the ability to work at high pH a biosensor for GABA is proposed by coimmobilizing GABA-aminotransferase (GABA-T) and PaoABC in the osmium containing redox polymer.
Biosensors for the detection of benzaldehyde and g-aminobutyric acid (GABA) are reported using aldehyde oxidoreductase PaoABC from Escherichia coli immobilized in a polymer containing bound low potential osmium redox complexes. The electrically connected enzyme already electrooxidizes benzaldehyde at potentials below −0.15 V (vs. Ag|AgCl, 1 M KCl). The pH-dependence of benzaldehyde oxidation can be strongly influenced by the ionic strength. The effect is similar with the soluble osmium redox complex and therefore indicates a clear electrostatic effect on the bioelectrocatalytic efficiency of PaoABC in the osmium containing redox polymer. At lower ionic strength, the pH-optimum is high and can be switched to low pH-values at high ionic strength. This offers biosensing at high and low pH-values. A “reagentless” biosensor has been formed with enzyme wired onto a screen-printed electrode in a flow cell device. The response time to addition of benzaldehyde is 30 s, and the measuring range is between 10–150 µM and the detection limit of 5 µM (signal to noise ratio 3:1) of benzaldehyde. The relative standard deviation in a series (n = 13) for 200 µM benzaldehyde is 1.9%. For the biosensor, a response to succinic semialdehyde was also identified. Based on this response and the ability to work at high pH a biosensor for GABA is proposed by coimmobilizing GABA-aminotransferase (GABA-T) and PaoABC in the osmium containing redox polymer.
The inverse problem of determining the flow at the Earth's core-mantle boundary according to an outer core magnetic field and secular variation model has been investigated through a Bayesian formalism. To circumvent the issue arising from the truncated nature of the available fields, we combined two modeling methods. In the first step, we applied a filter on the magnetic field to isolate its large scales by reducing the energy contained in its small scales, we then derived the dynamical equation, referred as filtered frozen flux equation, describing the spatiotemporal evolution of the filtered part of the field. In the second step, we proposed a statistical parametrization of the filtered magnetic field in order to account for both its remaining unresolved scales and its large-scale uncertainties. These two modeling techniques were then included in the Bayesian formulation of the inverse problem. To explore the complex posterior distribution of the velocity field resulting from this development, we numerically implemented an algorithm based on Markov chain Monte Carlo methods. After evaluating our approach on synthetic data and comparing it to previously introduced methods, we applied it to a magnetic field model derived from satellite data for the single epoch 2005.0. We could confirm the existence of specific features already observed in previous studies. In particular, we retrieved the planetary scale eccentric gyre characteristic of flow evaluated under the compressible quasi-geostrophy assumption although this hypothesis was not considered in our study. In addition, through the sampling of the velocity field posterior distribution, we could evaluate the reliability, at any spatial location and at any scale, of the flow we calculated. The flow uncertainties we determined are nevertheless conditioned by the choice of the prior constraints we applied to the velocity field.
The new N-heterocyclic carbene (NHC) complex [PdCl2{(CN)(2)IMes}(PPh3)] (2) ({(CN)(2)IMes}: 4,5-dicyano-1,3-dimesitylimidazol-2-ylidene) and the NHC palladacycle [PdCl(dmba){(CN)(2)IMes}] (3) (dmba: N,N-dimethylbenzylamine) have been synthesized by thermolysis of 4,5-dicyano-1,3-dimesityl-2-(pentafluorophenyl) imidazoline (1) in the presence of suitable palladium(II) precursors. The acyclic complex 2 was formed by ligand exchange using the mononuclear precursor [PdCl2(PPh3)(2)] and the palladacycle 3 was formed by cleavage of the dinuclear chloro-bridged precursor [Pd(mu-Cl)(dmba)](2). The new NHC precursor 1-benzyl-4,5-dicyano-2-(pentafluorophenyl)-3-picolylimidazoline (5) was formed by condensation of pentafluorobenzaldehyde with N-benzyl-N'-picolyldiaminomaleonitrile (4). The NHC palladacycle [PdCl2{(CN)(2)IBzPic}] (6) ({(CN)(2)IBzPic}: 1-benzyl-4,5-dicyano-3-picolylimidazol-2-ylidene) was prepared by in situ thermolysis of 5 in the presence of [PdCl2(PhCN)(2)]. The three palladium(II) complexes were characterized by NMR and IR spectroscopy, mass spectrometry and elemental analysis. In addition, the molecular structures of 2 and 3 were determined by X-ray diffraction. The pi-acidity of (CN)(2)IBzPic was compared with (CN)(2)IMes and perviously reported pi-acidic imidazol-2-ylidenes by NBO analysis. The Mizoroki-Heck (MH) reactions of various aryl halides with n-butyl acrylate were performed in the presence of complexes 2, 3 and 6. The new precatalysts showed high activity in the MH reactions giving good-to-excellent product yields with 0.1 mol-% pre-catalyst. The nature of the catalytically active species of 2, 3 and 6 was investigated by poisoning experiments with mercury and transmission electron microscopy. It was found that palladium nanoparticles formed from the precatalysts were involved in the catalytic process.