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1. Банковское право как отрасль права 2. Предмет, метод и система банковского права 3. Источники банковского права
1 Международное право прав человека 2 Право международной безопасности
1. Предмет международного частного права 2. Понятие международного частного права 3. Развитие МЧП 4. Содержание МЧП 5. Источники МЧП 6. Коллизионные нормы 7. Обратная отсылка и отсылка к праву третьего государства (renvoi) 8. Проблема квалификации в МЧП 9. Применение иностранного права, установление содержания иностранного права 10. Оговорка о публичном порядке 11. Императивные нормы 12. Основные коллизионные принципы
Migration and development in Senegal : a system dynamics analysis of the feedback relationships
(2011)
This thesis investigates the reciprocal relationship between migration and development in Senegal. Therewith, it contributes to the debate as to whether migration in developing countries enhances or rather impedes the development process. Even though extensive and controversial discussions can be found in the scientific literature regarding the impact of migration on development, research has scarcely examined the feedback relationships between migration and development. Science however agrees with both the fact that migration affects development as well as that the level of development in a country determines migration behaviour. Thus, both variables are neither dependent nor independent, but endogenous variables influencing each other and producing behavioural pattern that cannot be investigated using a static and unidirectional approach. On account of this, the thesis studies the feedback mechanisms existing between migration and development and the behavioural pattern generated by the high interdependence in order to be able to draw conclusions concerning the impact of changes in migration behaviour on the development process. To explore these research questions, the study applies the computer simulation method ‘System Dynamics’ and amplifies the simulation model for national development planning called ‘Threshold 21’ (T21), representing development processes endogenously and integrating economic, social and environmental aspects, using a structure that portrays the reasons and consequences of migration. The model has been customised to Senegal, being an appropriate representative of the theoretical interesting universe of cases. The comparison of the model generated scenarios - in which the intensity of emigration, the loss and gain of education, the remittances or the level of dependence changes - facilitates the analysis. The present study produces two important results. The first outcome is the development of an integrative framework representing migration and development in an endogenous way and incorporating several aspects of different theories. This model can be used as a starting point for further discussions and improvements and it is a fairly relevant and useful result against the background that migration is not integrated into most of the development planning tools despite its significant impact. The second outcome is the gained insights concerning the feedback relations between migration and development and the impact of changes in migration on development. To give two examples: It could be found that migration impacts development positively, indicated by HDI, but that the dominant behaviour of migration and development is a counteracting behaviour. That means that an increase in emigration leads to an improvement in development, while this in turn causes a decline in emigration, counterbalancing the initial increase. Another insight concerns the discovery that migration causes a decline in education in the short term, but leads to an increase in the long term, after approximately 25 years - a typical worse-before-better behaviour. From these and further observations, important policy implications can be derived for the sending and receiving countries. Hence, by overcoming the unidirectional perspective, this study contributes to an improved understanding of the highly complex relationship between migration and development and their feedback relations.
Species respond to environmental change by dynamically adjusting their geographical ranges. Robust predictions of these changes are prerequisites to inform dynamic and sustainable conservation strategies. Correlative species distribution models (SDMs) relate species’ occurrence records to prevailing environmental factors to describe the environmental niche. They have been widely applied in global change context as they have comparably low data requirements and allow for rapid assessments of potential future species’ distributions. However, due to their static nature, transient responses to environmental change are essentially ignored in SDMs. Furthermore, neither dispersal nor demographic processes and biotic interactions are explicitly incorporated. Therefore, it has often been suggested to link statistical and mechanistic modelling approaches in order to make more realistic predictions of species’ distributions for scenarios of environmental change. In this thesis, I present two different ways of such linkage. (i) Mechanistic modelling can act as virtual playground for testing statistical models and allows extensive exploration of specific questions. I promote this ‘virtual ecologist’ approach as a powerful evaluation framework for testing sampling protocols, analyses and modelling tools. Also, I employ such an approach to systematically assess the effects of transient dynamics and ecological properties and processes on the prediction accuracy of SDMs for climate change projections. That way, relevant mechanisms are identified that shape the species’ response to altered environmental conditions and which should hence be considered when trying to project species’ distribution through time. (ii) I supplement SDM projections of potential future habitat for black grouse in Switzerland with an individual-based population model. By explicitly considering complex interactions between habitat availability and demographic processes, this allows for a more direct assessment of expected population response to environmental change and associated extinction risks. However, predictions were highly variable across simulations emphasising the need for principal evaluation tools like sensitivity analysis to assess uncertainty and robustness in dynamic range predictions. Furthermore, I identify data coverage of the environmental niche as a likely cause for contrasted range predictions between SDM algorithms. SDMs may fail to make reliable predictions for truncated and edge niches, meaning that portions of the niche are not represented in the data or niche edges coincide with data limits. Overall, my thesis contributes to an improved understanding of uncertainty factors in predictions of range dynamics and presents ways how to deal with these. Finally I provide preliminary guidelines for predictive modelling of dynamic species’ response to environmental change, identify key challenges for future research and discuss emerging developments.
The ability of some plant species to dominate communities in new biogeographical ranges has been attributed to an innate higher competitive ability and release from co-evolved specialist enemies. Specifically, invasive success in the new range might be explained by release from biotic negative soil-feedbacks, which control potentially dominant species in their native range. To test this hypothesis, we grew individuals from sixteen phylogenetically paired European grassland species that became either invasive or naturalized in new ranges, in either sterilized soil or in sterilized soil with unsterilized soil inoculum from their native home range. We found that although the native members of invasive species generally performed better than those of naturalized species, these native members of invasive species also responded more negatively to native soil inoculum than did the native members of naturalized species. This supports our hypothesis that potentially invasive species in their native range are held in check by negative soil-feedbacks. However, contrary to expectation, negative soil-feedbacks in potentially invasive species were not much increased by interspecific competition. There was no significant variation among families between invasive and naturalized species regarding their feedback response (negative vs. neutral). Therefore, we conclude that the observed negative soil feedbacks in potentially invasive species may be quite widespread in European families of typical grassland species.
In high-value sweet cherry (Prunus avium), the red coloration - determined by the anthocyanins content - is correlated with the fruit ripeness stage and market value. Non-destructive spectroscopy has been introduced in practice and may be utilized as a tool to assess the fruit pigments in the supply chain processes. From the fruit spectrum in the visible (Vis) wavelength range, the pigment contents are analyzed separately at their specific absorbance wavelengths.
A drawback of the method is the need for re-calibration due to varying optical properties of the fruit tissue. In order to correct for the scattering differences, most often the spectral intensity in the visible spectrum is normalized by wavelengths in the near infrared (NIR) range, or pre-processing methods are applied in multivariate calibrations.
In the present study, the influence of the fruit scattering properties on the Vis/NIR fruit spectrum were corrected by the effective pathlength in the fruit tissue obtained from time-resolved readings of the distribution of time-of-flight (DTOF). Pigment analysis was carried out according to Lambert-Beer law, considering fruit spectral intensities, effective pathlength, and refractive index. Results were compared to commonly applied linear color and multivariate partial least squares (PLS) regression analysis. The approaches were validated on fruits at different ripeness stages, providing variation in the scattering coefficient and refractive index exceeding the calibration sample set.
In the validation, the measuring uncertainty of non-destructively analyzing fruits with Vis/NIR spectra by means of PLS or Lambert-Beer in comparison with combined application of Vis/NIR spectroscopy and DTOF measurements showed a dramatic bias reduction as well as enhanced coefficients of determination when using both, the spectral intensities and apparent information on the scattering influence by means of DTOF readings. Corrections for the refractive index did not render improved results.
The morphological features in the deviations of the total electron content (TEC) of the ionosphere from the background undisturbed state as possible precursors of the earthquake of January 12, 2010 (21:53 UT (16:53 LT), 18.46A degrees N, 72.5A degrees W, 7.0 M) in Haiti are analyzed. To identify these features, global and regional differential TEC maps based on global 2-h TEC maps provided by NASA in the IONEX format were plotted. For the considered earthquake, long-lived disturbances, presumably of seismic origin, were localized in the near-epicenter area and were accompanied by similar effects in the magnetoconjugate region. Both decreases and increases in the local TEC over the period from 22 UT of January 10 to 08 UT of January 12, 2010 were observed. The horizontal dimensions of the anomalies were similar to 40A degrees in longitude and similar to 20A degrees in latitude, with the magnitude of TEC disturbances reaching similar to 40% relative to the background near the epicenter and more than 50% in the magnetoconjugate area. No significant geomagnetic disturbances within January 1-12, 2010 were observed, i.e., the detected TEC anomalies were manifestations of interplay between processes in the lithosphere-atmosphere-ionosphere system.
- Einleitung - Die Situation der Universität Leipzig nach der Einnahme durch die Schweden - Balance zwischen legitimer und faktischer Herrschaft - Streit mit Rat und Bürgerschaft - Das Verhältnis der Universität zu den schwedischen Besatzern - Positive Auswirkungen der Besatzung auf die Universität Leipzig - Fazit
The languages of the world exhibit a range of formal phenomena (e.g. accenting, syntactic reordering and morphological marking) that are commonly linked to the information-structural notion of focus. Crucially, there does not seem to be a one-to-one mapping between particular formal features (focus marking devices) and focus, neither from a cross-linguistic perspective, nor within individual languages. This raises the question of what is actually being expressed if we say that a constituent is focused in a particular language, and whether, or to what extent, the same semantic or pragmatic content is formally expressed by focus-marking across languages. This special issue addresses the question of focus and its grammatical realization from a number of theoretical and empirical perspectives. In this introductory article we elaborate on this question by making an explicit proposal about what we take to be the correct way of thinking about the information-structural category of focus and its formal realization. In the first part, we introduce a unified semantico-pragmatic perspective on focus in terms of alternatives and possible worlds. In the second part, we present a cursory cross-linguistic overview of focus marking strategies as found in the languages of the world. Finally, in the third part, we discuss the connection between the notion of focus, different pragmatic uses of focus and different focus marking strategies employed in the grammars of natural languages. (C) 2011 Elsevier B.V. All rights reserved.
On the functional architecture of DP and the feature content of pronominal quantifiers in Low German
(2011)
The article investigates the functional architecture of complex pronominal quantifying expressions (PQEs) in Low German, such as jeder-een 'everyone' and keen-een 'no-one', which provide overt evidence for a Num-projection, situated between the NP- and DP-layer. The feature specification of Num as [+lattice] or [-lattice] is responsible for whether the DP denotes into the domain of atomic or mass/plural entities, respectively. In the case of complex PQEs, the syntactic Num-head hosts the overt element een 'a, one', which carries a [-lattice] feature, thus ensuring that the PQE ranges exclusively over the domain of atomic entities, but not mass or plural entities. The Num-head een differs from its simplex counterpart wat 'something', which is analyzed as an NP-proform with an underspecified [lattice]-feature. As a result, wat can range over atomic and mass domains alike. In the final part of the article, it is argued that wat is also underspecified for the operator feature [rel/wh], for which reason it can also function as an interrogative expression (what) and as a relative pronoun (which), respectively, depending on the syntactic context. Throughout the article, the Low German data are compared with relevant data from other German dialects and Germanic and Romance languages, pointing out similarities and differences in the syntactic structure and feature content of PQEs across these languages and dialects.
The grammatical expression of focus in West Chadic variation and uniformity in and across languages
(2011)
The article provides an overview of the grammatical realization of focus in four West Chadic languages (Chadic, Afro-Asiatic). The languages discussed exhibit an intriguing crosslinguistic variation in the realization of focus, both among themselves as well as compared to European intonation languages. They also display language-internal variation in the formal realization of focus. The West Chadic languages differ widely in their ways of expressing focus, which range from syntactic over prosodic to morphological devices. In contrast to European intonation languages, the focus marking systems of the West Chadic languages are inconsistent in that focus is often not grammatically expressed, but these inconsistencies are shown to be systematic. Subject foci (contrastive or not) and contrastive nonsubject foci are always grammatically marked, whereas information focus on nonsubjects need not be marked as such. The absence of formal focus marking supports pragmatic theories of focus in terms of contextual resolution. The special status of focused subjects and contrastive foci is derived from the Contrastive Focus Hypothesis, which requires unexpected foci and unexpected focus contents to be marked as such, together with the assumption that canonical subjects in West Chadic receive a default interpretation as topics. Finally, I discuss certain focus ambiguities which are not attested in intonation languages, nor do they follow on standard accounts of focus marking, but which can be accounted for in terms of constraint interaction in the formal expression of focus.
The article provides an overview of the grammatical realization of focus in four West Chadic languages (Chadic, Afro-Asiatic). The languages discussed exhibit an intriguing crosslinguistic variation in the realization of focus, both among themselves as well as compared to European intonation languages. They also display language-internal variation in the formal realization of focus. The West Chadic languages differ widely in their ways of expressing focus, which range from syntactic over prosodic to morphological devices. In contrast to European intonation languages, the focus marking systems of the West Chadic languages are inconsistent in that focus is often not grammatically expressed, but these inconsistencies are shown to be systematic. Subject foci (contrastive or not) and contrastive nonsubject foci are always grammatically marked, whereas information focus on nonsubjects need not be marked as such. The absence of formal focus marking supports pragmatic theories of focus in terms of contextual resolution. The special status of focused subjects and contrastive foci is derived from the Contrastive Focus Hypothesis, which requires unexpected foci and unexpected focus contents to be marked as such, together with the assumption that canonical subjects in West Chadic receive a default interpretation as topics. Finally, I discuss certain focus ambiguities which are not attested in intonation languages, nor do they follow on standard accounts of focus marking, but which can be accounted for in terms of constraint interaction in the formal expression of focus.
Article 22
(2011)
Das vorliegende Heft 16 der Reihe Studien zu Grund- und Menschenrechten enthält den Tagungsband zum Workshop „Mechanismen zur Folterverhütung im Vergleich“, welcher am 6. und 7. Oktober 2010 in Potsdam stattfand und die unterschiedlichen Mechanismen zur Folterprävention auf universeller, regionaler und nationaler Ebene beleuchtete.
Article 1 A, para. 2
(2011)
Article 33, para. 2
(2011)
Article 1 F
(2011)
Microcystins are cyanobacterial toxins that represent a serious threat to drinking water and recreational lakes worldwide. Here, we show that microcystin fulfils an important function within cells of its natural producer Microcystis. The microcystin deficient mutant Delta mcyB showed significant changes in the accumulation of proteins, including several enzymes of the Calvin cycle, phycobiliproteins and two NADPH-dependent reductases. We have discovered that microcystin binds to a number of these proteins in vivo and that the binding is strongly enhanced under high light and oxidative stress conditions. The nature of this binding was studied using extracts of a microcystin-deficient mutant in vitro. The data obtained provided clear evidence for a covalent interaction of the toxin with cysteine residues of proteins. A detailed investigation of one of the binding partners, the large subunit of RubisCO showed a lower susceptibility to proteases in the presence of microcystin in the wild type. Finally, the mutant defective in microcystin production exhibited a clearly increased sensitivity under high light conditions and after hydrogen peroxide treatment. Taken together, our data suggest a protein-modulating role for microcystin within the producing cell, which represents a new addition to the catalogue of functions that have been discussed for microbial secondary metabolites.
The thermal behavior of poly(methoxydiethylenglycol acrylate) (PMDEGA) is studied in thin hydrogel films on solid supports and is compared with the behavior in aqueous solution. The PMDEGA hydrogel film thickness is varied from 2 to 422 nm. Initially, these films are homogenous, as measured with optical microscopy, atomic force microscopy, X-ray reflectivity, and grazing-incidence small-angle X-ray scattering (GISAXS). However, they tend to de-wet when stored under ambient conditions. Along the surface normal, no long-ranged correlations between substrate and film surface are detected with GISAXS, due to the high mobility of the polymer at room temperature. The swelling of the hydrogel films as a function of the water vapor pressure and the temperature are probed for saturated water vapor pressures between 2,380 and 3,170 Pa. While the swelling capability is found to increase with water vapor pressure, swelling in dependence on the temperature revealed a collapse phase transition of a lower critical solution temperature type. The transition temperature decreases from 40.6 A degrees C to 36.6 A degrees C with increasing film thickness, but is independent of the thickness for very thin films below a thickness of 40 nm. The observed transition temperature range compares well with the cloud points observed in dilute (0.1 wt.%) and semi-dilute (5 wt.%) solution which decrease from 45 A degrees C to 39 A degrees C with increasing concentration.
We study the properties of classical and quantum strongly nonlinear chains by means of extensive numerical simulations. Due to strong nonlinearity, the classical dynamics of such chains remains chaotic at arbitrarily low energies. We show that the collective excitations of classical chains are described by sound waves whose decay rate scales algebraically with the wave number with a generic exponent value. The properties of the quantum chains are studied by the quantum Monte Carlo method and it is found that the low-energy excitations are well described by effective phonon modes with the sound velocity dependent on an effective Planck constant. Our results show that at low energies the quantum effects lead to a suppression of chaos and drive the system to a quasi-integrable regime of effective phonon modes.
The open source computational fluid dynamics (CFD) wind model (CFD-WEM) for wind erosion research in the Xilingele grassland in Inner Mongolia (autonomous region, China) is compared with two open source CFD models Gerris and OpenFOAM. The evaluation of these models was made according to software technology, implemented methods, handling, accuracy and calculation speed. All models were applied to the same wind tunnel data set. Results show that the simplest CFD-WEM has the highest calculation speed with acceptable accuracy, and the most powerful OpenFOAM produces the simulation with highest accuracy and the lowest calculation speed. Gerris is between CFD-WEM and OpenFOAM. It calculates faster than OpenFOAM, and it is capable to solve different CFD problems. CFD-WEM is the optimal model to be further developed for wind erosion research in Inner Mongolia grassland considering its efficiency and the uncertainties of other input data. However, for other applications using CFD technology, Gerris and OpenFOAM can be good choices. This paper shows the powerful capability of open source CFD software in wind erosion study, and advocates more involvement of open source technology in wind erosion and related ecological researches.
In eukaryotes, the transcription of tRNA genes is initiated by the concerted action of transcription factors IIIC (TFIIIC) and IIIB (TFIIIB) which direct the recruitment of polymerase III. While TFIIIC recognizes highly conserved, intragenic promoter elements, TFIIIB binds to the non-coding 5'-upstream regions of the tRNA genes. Using a systematic bioinformatic analysis of 11 multicellular eukaryotic genomes we identified a highly conserved TATA motif followed by a CAA-motif in the tRNA upstream regions of all plant genomes. Strikingly, the 5'-flanking tRNA regions of the animal genomes are highly heterogeneous and lack a common conserved sequence signature. Interestingly, in the animal genomes the tRNA species that read the same codon share conserved motifs in their upstream regions. Deep-sequencing analysis of 16 human tissues revealed multiple splicing variants of two of the TFIIIB subunits, Bdp1 and Brf1, with tissue-specific expression patterns. These multiple forms most likely modulate the TFIIIB-DNA interactions and explain the lack of a uniform signature motif in the tRNA upstream regions of animal genomes. The anticodon-dependent 5'-flanking motifs provide a possible mechanism for independent regulation of the tRNA transcription in various human tissues.
Folding at the birth of the nascent chain: coordinating translation with co-translational folding
(2011)
In the living cells, the folding of many proteins is largely believed to begin co-translationally, during their biosynthesis at the ribosomes. In the ribosomal tunnel, the nascent peptide may establish local interactions and stabilize alpha-helical structures. Long-range contacts are more likely outside the ribosomes after release of larger segments of the nascent chain. Examples suggest that domains can attain native-like structure on the ribosome with and without population of folding intermediates. The co-translational folding is limited by the speed of the gradual extrusion of the nascent peptide which imposes conformational restraints on its folding landscape. Recent experimental and in silico modeling studies indicate that translation kinetics fine-tunes co-translational folding by providing a time delay for sequential folding of distinct portions of the nascent chain.
Mit dem Amtsantritt von Präsident Santos 2010 hat sich das politische Klima in Kolumbien spürbar verändert. Der ehemalige Verteidigungsminister Uribes distanziert sich von seinem einstigen Vorgesetzten: Außenpolitisch sucht Santos Kontakt zu den Nachbarstaaten, im Land selbst darf wieder über den bewaffneten Konflikt mit der Guerilla diskutiert werden. An der neoliberalen Wirtschaftspolitik hält jedoch auch Präsident Santos fest.
Molecular brush diblock copolymers were synthesized by the orthogonal overlay of the RAFT (reversible addition-fragmentation chain transfer), the ATRP (atom transfer radical polymerization), and the NMP (nitroxide-mediated polymerization) techniques. This unique combination enabled the synthesis of the complex amphiphilic polymers without the need of postpolymerization modifications, using a diblock copolymer intermediate made from two selectively addressable inimers and applying a sequence of four controlled free radical polymerization steps in total. The resulting polymers are composed of a thermosensitive poly(N-isopropylacrylamide) brush as hydrophilic block and a polystyrene brush as hydrophobic block, thus translating the structure of the established amphiphilic diblock copolymers known as macro surfactants to the higher size level of "giant surfactants". The dual molecular brushes and the aggregates formed on ultra flat solid substrates were visualized by scanning force microscopy (SFM).
The combination of two techniques of controlled free radical polymerization, namely the reversible addition fragmentation chain transfer (RAFT) and the atom transfer radical polymerization (ATRP) techniques, together with the use of a macromonomer allowed the synthesis of symmetrical triblock copolymers, designed as amphiphilic dual brushes. One type of brush was made of poly(n-butyl acrylate) as soft hydrophobic block, i.e. characterized by a low glass transition temperature, while the other one was made of hydrophilic poly(ethylene glycol) (PEG). The new triblock polymers represent "giant surfactants" according to their molecular architecture. The hydrophobic and hydrophilic blocks microphase separate in the bulk. In aqueous solution, they aggregate into globular micellar aggregates, their size being determined by the length of the stretched polymer molecules. As determined by the combination of various scattering techniques for the dual brush copolymer, a rather compact structure is formed, which is dominated by the large hydrophobic poly(n-butyl acrylate) block. The aggregation number for the dual brush is about 10 times larger than for the "semi-brush" precursor copolymer, due to the packing requirements for the much bulkier hydrophobic core. On mica surfaces the triblock copolymers adsorb with worm-like backbones and stretched out side chains.
Background and objective Whether treatment with vitamin D receptor activators contributes to cardiovascular disease in patients with chronic kidney disease is a matter of debate. We studied mechanisms involved in vitamin D-related vascular calcifications in vivo and in vitro.
Methods Aortic calcifications were induced in subtotally nephrectomized (SNX) rats by treatment with a high dose (0.25 mu g/kg per day) of 1,25-dihydroxyvitamin D-3 (calcitriol) given for 6 weeks. Likewise, primary rat vascular smooth muscle cells (VSMCs) were incubated with calcitriol at concentrations ranging from 10(-11) to 10(-7) mol/l. Immunohistochemistry revealed that the aortic expression of osteopontin, osteocalcin and bone sialoprotein was significantly increased in calcitriol-treated SNX rats compared to untreated SNX controls. In addition, aortic expression of the transient receptor potential vanilloid calcium channel 6 (TRPV6) and calbindin D9k was significantly up-regulated by treatment with calcitriol. Furthermore, calcitriol significantly increased expression of the osteogenic transcription factor osterix. In-vitro studies showed similar results, confirming that these effects could be attributed to treatment with calcitriol.
Conclusions High-dose calcitriol treatment induces an osteoblastic phenotype in VSMC both in SNX rats and in vitro, associated with up-regulation of proteins regulating mineralization and calcium transport, and of the osteogenic transcription factor osterix.
Influence of tyrosine-derived moieties and drying conditions on the formation of helices in gelatin
(2011)
The single and triple helical organization of protein chains strongly influences the mechanical properties of gelatin-based materials. A chemical method for obtaining different degrees of helical organization in gelatin is covalent functionalization, while a physical method for achieving the same goal is the variation of the drying conditions of gelatin solutions. Here we explored how the introduction of desaminotyrosine (DAT) and desaminotyrosyl tyrosine (DATT) linked to lysine residues of gelatin influenced the kinetics and thermodynamic equilibrium of the helicalization process of single and triple helices following different drying conditions. Drying at a temperature above. the helix-to-coil transition temperature of gelatin (T > T-c, called nu(short)) generally resulted in gelatins with relatively lower triple helical content (X-c,X-t = 1-2%) than lower temperature drying (T < T-c, called nu(long)) (X-c,X-t = 8-10%), where the DAT(T) functional groups generally disrupted helix formation. While different helical contents affected the thermal transition temperatures only slightly, the mechanical properties were strongly affected for swollen hydrogels (E = 4-13 kPa for samples treated by nu(long) and E = 120-700 kPa for samples treated by nu(short)). This study shows that side group functionalization and different drying conditions are viable options to control the helicalization and macroscopic properties of gelatin-based materials.
Biomaterials are used in regenerative medicine for induced autoregeneration and tissue engineering. This is often challenging, however, due to difficulties in tailoring and controlling the respective material properties. Since functionalization is expected to offer better control, in this study gelatin chains were modified with physically interacting groups based on tyrosine with the aim of causing the formation of physical crosslinks. This method permits application-specific properties like swelling and better tailoring of mechanical properties. The design of the crosslink strategy was supported by molecular dynamic (MD) simulations of amorphous bulk models for gelatin and functionalized gelatins at different water contents (0.8 and 25 wt.-%). The results permitted predictions to be formulated about the expected crosslink density and its influence on equilibrium swelling behavior and on elastic material properties. The models of pure gelatin were used to validate the strategy by comparison between simulated and experimental data such as density, backbone conformation angle distribution, and X-ray scattering spectra. A key result of the simulations was the prediction that increasing the number of aromatic functions attached to the gelatin chain leads to an increase in the number of physical netpoints observed in the simulated bulk packing models. By comparison with the Flory-Rehner model, this suggested reduced equilibrium swelling of the functionalized materials in water, a prediction that was subsequently confirmed by our experimental work. The reduction and control of the equilibrium degree of swelling in water is a key criterion for the applicability of functionalized gelatins when used, for example, as matrices for induced autoregeneration of tissues.
We report on the interaction of cationic azobenzene-containing surfactant with DNA investigated by absorption and fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy. The properties of the surfactant can be controlled with light by reversible switching of the azobenzene unit, incorporated into the surfactant tail, between a hydrophobic trans (visible irradiation) and a hydrophilic cis (UV irradiation) configuration. The influence of the trans-cis isomerization of the azobenzene on the compaction process of DNA molecules and the role of both isomers in the formation and colloidal stability of DNA-surfactant complexes is discussed. It is shown that the trans isomer plays a major role in the DNA compaction process. The influence of the cis isomer on the DNA coil configuration is rather small. The construction of a phase diagram of the DNA concentration versus surfactant/DNA charge ratio allows distancing between three major phases: colloidally stable and unstable compacted globules, and extended coil conformation. There is a critical concentration of DNA above which the compacted globules can be hindered from aggregation and precipitation by adding an appropriate amount of the surfactant in the trans configuration. This is because of the compensation of hydrophobicity of the globules with an increasing amount of the surfactant. Below the critical DNA concentration, the compacted globules are colloidally stable and can be reversibly transferred with light to an extended coil state.
The dynamical structure of genetic networks determines the occurrence of various biological mechanisms, such as cellular differentiation. However, the question of how cellular diversity evolves in relation to the inherent stochasticity and intercellular communication remains still to be understood. Here, we define a concept of stochastic bifurcations suitable to investigate the dynamical structure of genetic networks, and show that under stochastic influence, the expression of given proteins of interest is defined via the probability distribution of the phase variable, representing one of the genes constituting the system. Moreover, we show that under changing stochastic conditions, the probabilities of expressing certain concentration values are different, leading to different functionality of the cells, and thus to differentiation of the cells in the various types.
Commercially available 1,2-PB was transformed into a well-defined reactive intermediate by quantitative bromination. The brominated polymer was used as a polyfunctional macroinitiator for the cationic ring-opening polymerization of 2-ethyl-2-oxazoline to yield a water-soluble brush polymer. Nucleophilic substitution of bromide by 1-methyl imidazole resulted in the formation of polyelectrolyte copolymers consisting of mixed units of imidazolium, bromo, and double bond. These copolymers, which were soluble in water without forming aggregates, were used as stabilizers in the heterophase polymerization of styrene and were also studied for their ionic conducting properties.
Bicyclic carbohydrate 1,2-lactones have been synthesized in only two steps and high yields by saponification and subsequent cyclization from known malonate addition products to glycals. The gluco-configured lactone serves as an important precursor for diversity-oriented syntheses. Thus, stereoselective opening of the lactone ring was realized with various nucleophiles in the presence of Sc(OTf)(3). This enabled the introduction of different substituents at the anomeric position, to afford a broad variety of 1-functionalized carbohydrates. On the other hand, stereoselective alpha-substitution of the gluco-configured lactone with different electrophiles and subsequent ring opening gives a collection of 2-functionalized saccharides. More than 30 products have been isolated in analytically pure form, and their configurations were unequivocally established by various NMR methods. Thus, carbohydrate 1,2-lactones are attractive precursors for the stereoselective synthesis of diverse saccharides.
Surface uplift at the northern margin of the Central Anatolian Plateau (CAP) is integrally tied to the evolution of the Central Pontides (CP), between the North Anatolian Fault (NAF) and the Black Sea. Our regional morphometric and plate kinematic analyses reveal topographic anomalies, steep channel gradients, and local high relief areas as indicators of ongoing differential surface uplift, which is higher in the western CP compared to the eastern CP and fault-normal components of geodetic slip vectors and the character of tectonic activity of the NAF suggest that stress is accumulated in its broad restraining bend. Seismic reflection and structural field data show evidence for a deep structural detachment horizon responsible for the formation of an actively northward growing orogenic wedge with a positive flower-structure geometry across the CP and the NAF. Taken together, the tectonic, plate kinematic, and geomorphic observations imply that the NAF is the main driving mechanism for wedge tectonics and uplift in the CP. In addition, the NAF Zone defines the boundary between the extensional CAP and the contractional CP. The syntectonic deposits within inverted intermontane basins and deeply incised gorges suggest that the formation of relief, changes in sedimentary dynamics, and > 1 km fluvial incision resulted from accelerated uplift starting in the early Pliocene. The Central Pontides thus provide an example of an accretionary wedge with surface-breaking faults that play a critical role in mountain building processes, sedimentary basin development, and ensuing lateral growth of a continental plateau since the end of the Miocene.
In this article, we discuss the notions of experts and expertise in resource discovery in the context of collaborative tagging systems. We propose that the level of expertise of a user with respect to a particular topic is mainly determined by two factors. First, an expert should possess a high-quality collection of resources, while the quality of a Web resource in turn depends on the expertise of the users who have assigned tags to it, forming a mutual reinforcement relationship. Second, an expert should be one who tends to identify interesting or useful resources before other users discover them, thus bringing these resources to the attention of the community of users. We propose a graph-based algorithm, SPEAR (spamming-resistant expertise analysis and ranking), which implements the above ideas for ranking users in a folksonomy. Our experiments show that our assumptions on expertise in resource discovery, and SPEAR as an implementation of these ideas, allow us to promote experts and demote spammers at the same time, with performance significantly better than the original hypertext-induced topic search algorithm and simple statistical measures currently used in most collaborative tagging systems.
We report on the redox behaviour of the microperoxidase-11 (MP-11) which has been electrostatically immobilized in a matrix of chitosan-embedded gold nanoparticles on the surface of a glassy carbon electrode. MP-11 contains a covalently bound heme c as the redox active group that exchanges electrons with the electrode via the gold nanoparticles. Electroactive surface concentration of MP-11 at high scan rate is between 350+/-50 pmol cm(-2), which reflects a multilayer process. The formal potential (E degrees') of MP-11 in the gold nanoparticles-chitosan film was estimated to be -(267.7+/-2.9) mV at pH 7.0. The heterogeneous electron transfer rate constant (k(s)) starts at 1.21 s(-1) and levels off at 6.45 s(-1) in the scan rate range from 0.1 to 2.0 V s(-1). Oxidation and reduction of MP-11 by hydrogen peroxide and superoxide, respectively have been coupled to the direct electron transfer of MP-11.