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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
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.
Article 22
(2011)
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.
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.
Enzyme electrode for aromatic compounds exploiting the catalytic activities of microperoxidase-11
(2011)
Microperoxidase-11 (MR-11) which has been immobilised in a matrix of chitosan-embedded gold nanoparticles on the surface of a glassy carbon electrode catalyzes the conversion of aromatic substances. This peroxide-dependent catalysis of microperoxidase has been applied in an enzyme electrode for the first time to indicate aromatic compounds such as aniline. 4-fluoroaniline, catechol and p-aminophenol. The electrode signal is generated by the cathodic reduction of the quinone or quinoneimine which is formed in the presence of both MP-II and peroxide from the substrate. The same sensor principle will be extended to aromatic drugs.
We report on the ionothermal synthesis of porous carbon materials from a variety of carbohydrate precursors (i.e. D-glucose, D-fructose, D-xylose, and starch) using 1-butyl-3-methylimidazolium tetrachloroferrate(III), [Bmim][FeCl(4)] as a reusable solvent and catalyst. The carbon materials derived from these different carbohydrates are similar in terms of particle size and chemical composition, possessing relatively high surface areas from 44 to 155 m(2) g(-1) after ionothermal processing, which can be significantly increased to > 350 m(2) g(-1) by further thermal treatment (e. g. post-carbonization at 750 degrees C). CO(2) and N(2) sorption analysis, combined with Hg intrusion porosimetry, reveals a promising hierarchical pore structuring to these carbon materials. The ionic liquid [Bmim][FeCl(4)] has a triple role: it acts as both a soft template to generate the characterized pore structuring, solvent and as a catalyst resulting in enhanced ionothermal carbon yields. Importantly from a process point of view, the ionic liquid can be successfully recovered and reused. The current work shows that ionothermal synthesis has the potential to be an effective, low cost, and green reusable synthetic route towards sustainable porous carbon materials.
The iron-containing ionic liquids 1-butyl-3-methylimidazolium tetrachloroferrate(III) [C(4)mim][FeCl4] and 1-dodecyl-3-methylimidazolium tetrachloroferrate(III) [C(12)mim][FeCl4] exhibit a thermally induced demixing with water (thermomorphism). The phase separation temperature varies with IL weight fraction in water and can be tuned between 100 degrees C and room temperature. The reversible lower critical solution temperature (LCST) is only observed at IL weight fractions below ca. 35% in water. UV/Vis, IR, and Raman spectroscopy along with elemental analysis prove that the yellow-brown liquid phase recovered after phase separation is the starting IL [C(4)mim][FeCl4] and [C(12)mim][FeCl4], respectively. Photometry and ICP-OES show that about 40% of iron remains in the water phase upon phase separation. Although the process is thus not very efficient at the moment, the current approach is the first example of an LCST behavior of a metal-containing IL and therefore, although still inefficient, a prototype for catalyst removal or metal extraction.
Our goal was to reconstruct the late eighteenth century forest vegetation of the Prignitz region (NE Germany) at a scale of 1:50,000. We also wanted to relate the historical forest vegetation to the actual and potential natural vegetation. For these purposes, we selected 15 woody species and transferred relevant data found in historical records from various sources together with the recent localities of (very) old individuals belonging to these woody species into ArcView GIS. Following multi-step data processing including the generation of a point density layer using a moving window with kernel estimation and derivation of vegetation units applying Boolean algebra rules together with information on site conditions, we derived 17 forest communities corresponding to the potential natural vegetation. We were able to reconstruct the historical forest vegetation for 90% of the forest area ca. 1780. Only two of the 17 forest communities covered large parts of the forested area. The oak forest with Agrostis capillaris covered about 44% of the total forest area, and alder forests on fenland made up about 37%. Oak-hornbeam forests with Stellaria holostea comprised slightly less than 6% of the forest area, while all other forest communities comprised less than 1%. The historical forest vegetation is more similar to the potential forest vegetation and quite different from the actual forest vegetation because coniferous tree species currently cover approximately two-thirds of the actual forest area. The most beneficial result of this study is the map of high-resolution historical vegetation units that may serve as the basis for various further studies, e.g., modelling long-term changes in biodiversity at the landscape scale.
Three different sizes of chitosan-capped Au nanoparticles were synthesized and were used to incorporate Agrocybe aegerita peroxygenase (AaeAPO) onto the surface of glassy carbon electrode. The direct electron transfer of AaeAPO was achieved in all films. The highest amount of electroactive enzyme and highest electron transfer rate constant k(s) of AaeAPO were obtained in the film with the smallest size of chitosan-capped Au nanoparticles.
In anaerobic solutions, quasi-reversible oxidation and reduction are obtained with a formal potential of -0.280V vs. Ag/AgCl 1 M KCl in 100 mM (pH 7.0) PBS at scan rate of 1 V s(-1). Bioelectrocatalytic reduction currents can be obtained with the AaeAPO-modified electrode on addition of hydrogen peroxide. This reaction was suppressed when sodium azide, an inhibitor of AaeAPO, was present. Furthermore, the peroxide-dependent conversion of aniline was characterized and it was found that a polymer product via p-aminophenol is formed. And the AaeAPO biosensor was applied to determine aniline and p-aminophenol.
We report on the detection of strongly varying intergalactic He II absorption in HST/COS spectra of two z(em) similar or equal to 3 quasars. From our homogeneous analysis of the He II absorption in these and three archival sightlines, we find a marked increase in the mean He II effective optical depth from <tau(eff, He II)> similar or equal to 1 at z similar or equal to 2.3 to <tau(eff, He II)> greater than or similar to 5 at z similar or equal to 3.2, but with a large scatter of 2 less than or similar to tau(eff, He II) less than or similar to 5 at 2.7 < z < 3 on scales of similar to 10 proper Mpc. This scatter is primarily due to fluctuations in the He II fraction and the He II-ionizing background, rather than density variations that are probed by the coeval Hi forest. Semianalytic models of He II absorption require a strong decrease in the He II-ionizing background to explain the strong increase of the absorption at z greater than or similar to 2.7, probably indicating He II reionization was incomplete at z(reion) greater than or similar to 2.7. Likewise, recent three-dimensional numerical simulations of He II reionization qualitatively agree with the observed trend only if He II reionization completes at z(reion) similar or equal to 2.7 or even below, as suggested by a large tau(eff, He II) greater than or similar to 3 in two of our five sightlines at z < 2.8. By doubling the sample size at 2.7 less than or similar to z less than or similar to 3, our newly discovered He II sightlines for the first time probe the diversity of the second epoch of reionization when helium became fully ionized.
Interannual rainfall variations in equatorial East Africa are tightly linked to the El Nino Southern Oscillation (ENSO), with more rain and flooding during El Nino and droughts in La Nina years, both having severe impacts on human habitation and food security. Here we report evidence from an annually laminated lake sediment record from southeastern Kenya for interannual to centennial-scale changes in ENSO-related rainfall variability during the last three millennia and for reductions in both the mean rate and the variability of rainfall in East Africa during the Last Glacial period. Climate model simulations support forward extrapolation from these lake sediment data that future warming will intensify the interannual variability of East Africa's rainfall.
Space is understood best through movement, and complex spaces require not only movement but navigation. The theorization of navigable space requires a conceptual representation of space which is adaptable to the great malleability of video game spaces, a malleability which allows for designs which combine spaces with differing dimensionality and even involve non-Euclidean configurations with contingent connectivity. This essay attempts to describe the structural elements of video game space and to define them in such a way so as to make them applicable to all video game spaces, including potential ones still undiscovered, and to provide analytical tools for their comparison and examination. Along with the consideration of space, there will be a brief discussion of navigational logic, which arises from detectable regularities in a spatial structure that allow players to understand and form expectations regarding a game’s spaces.
Einleitung
(2011)
Interindividual variability in the regulation of the human stress system accounts for a part of the individual's liability to stress-related diseases. These differences are influenced by environmental and genetic factors. Early childhood adversity is a well-studied environmental factor affecting an individual's stress response which has been shown to be modulated by gene environment interaction (GxE). Neuropeptide Y (NPY) plays a role in stress regulation and genetic variation in NPY may influence stress responses. In this study, we analyzed the association of a common variant in the NPY gene promoter, rs16147, with cortisol and ACTH responses to acute psychosocial stress in young adults from the Mannheim Study of Children at Risk (MARS), an ongoing epidemiological cohort study following the outcome of early adversity from birth into adulthood. We found evidence of a GxE interaction between rs16147 and early adversity significantly affecting HPA axis responses to acute psychosocial stress. These findings suggest that the neurobiological mechanisms linking early adverse experience and later neuroendocrine stress regulation are modulated by a gene variant whose functional relevance is documented by increasing convergent evidence from in vitro, animal and human studies.
Logic synthesis of speed independent circuits based on signal transition graph (STG) decomposition is a promising approach to tackle complexity problems like state-space explosion. Unfortunately, decomposition can result in components that in isolation have irreducible complete state coding conflicts. In earlier work, the authors showed how to resolve such conflicts by introducing internal communication between components, but only for very restricted specification structures. Here, they improve their former work by presenting algorithms for identifying delay transitions and inserting gyroscopes for specifications having a much more general structure. Thus, the authors are now able to synthesise controllers from real-life specifications. For all algorithms, they present correctness proofs and show their successful application to benchmarks, including very complex STGs arising in the context of control resynthesis.
A sediment core from a closed basin lake (Lake Kuhai) from the semi-arid northeastern Tibetan Plateau was analysed for its pollen record to infer Lateglacial and post glacial vegetation and climatic change. At Lake Kuhai five major vegetation and climate shifts could be identified: (1) a change from cold and dry to relatively warmer and more moist conditions at 14.8 cal ka BP: (2) a shift to conditions of higher effective moisture and a stepwise warmer climate at 13.6 cal ka BP; (3) a further shift with increased moisture but colder conditions at 7.0 cal ka BP; (4) a return to a significantly colder and drier phase at 6.3 cal ka BP; (5) and a change back to relatively moist conditions at 2.2 cal ka BP. To investigate the response of lake ecosystems to climatic changes, statistical comparisons were made between the lake Kuhai pollen record and a formerly published ostracod and sedimentary record from the same sediment core. Furthermore, the pollen and lacustrine proxies from lake Kuhai were compared to a previously published pollen and lacustrine record from the nearby Lake Koucha. Statistical comparisons were done using non-metric multidimensional scaling and Procrustes rotation. Differences between lacustrine and pollen responses within one site could be identified, suggesting that lacustrine proxies are partly influenced by in-lake or local catchment processes, whereas the terrestrial (pollen) proxy shows a regional climate signal. Furthermore, we found regional differences in proxy response between lake Kuhai and Lake Koucha. Both pollen records reacted in similar ways to major environmental changes, with minor differences in the timing and magnitude of these changes. The lacustrine records were very similar in their timing and magnitude of response to environmental changes; however, the nature of change was at times very distinct. To place the current study in the context of Holocene moisture evolution across the Tibetan Plateau, we applied a five-scale moisture index and average link clustering to all available continuous palaeo-climate records from the Tibetan Plateau to possibly find general patterns of moisture evolution on the Plateau. However, no common regional pattern of moisture evolution during the Holocene could be detected. We assign this to complex responses of different proxies to environmental and atmospheric changes in an already very heterogeneous mountain landscape where minor differences in elevation can cause strong variation in microenvironments.
A general mean annual temperature increase accompanied with substantial glacial retreat has been noted on the Tibetan Plateau during the last two centuries but most significantly since the mid 1950s. These climate trends are particularly apparent on the southeastern Tibetan Plateau. However, the Tibetan Plateau (due to its heterogeneous mountain landscape) has very complex and spatially differing temperature and precipitations patterns. As a result, intensive palaeolimnological investigations are necessary to decipher these climatic patterns and to understand ecological responses to recent environmental change. Here we present palaeolimnological results from a (210)Pb/(137)Cs-dated sediment core spanning approximately the last 200 years from a remote high-mountain lake (LC6 Lake, working name) on the southeastern Tibetan Plateau. Sediment profiles of diatoms, organic variables (TOC, C:N) and grain size were investigated. The (210)Pb record suggests a period of rapid sedimentation, which might be linked to major tectonic events in the region ca. 1950. Furthermore, unusually high (210)Pb supply rates over the last 50 years suggest that the lake has possibly been subjected to increasing precipitation rates, sediment focussing and/or increased spring thaw. The majority of diatom taxa encountered in the core are typical of slightly acidic to circumneutral, oligotrophic, electrolyte-poor lakes. Diatom species assemblages were rich, and dominated by Cyclotella sp., Achnanthes sp., Aulacoseira sp. and fragilarioid taxa. Diatom compositional change was minimal over the 200-year period (DCCA = 0.85 SD, p = 0.59); only a slightly more diverse but unstable diatom assemblage was recorded during the past 50 years. The results indicate that large-scale environmental changes recorded in the twentieth century (i.e. increased precipitation and temperatures) are likely having an affect on the LC6 Lake, but so far these impacts are more apparent on the lake geochemistry than on the diatom flora. Local and/or regional peculiarities, such as increasing precipitation and cloud cover, or localized climatic phenomena, such as negative climate feedbacks, might have offset the effects of increasing mean surface temperatures.
Rapid population growth and economic development have led to increased anthropogenic pressures on the Tibetan Plateau, causing significant land cover changes with potentially severe ecological consequences. To assess whether or not these pressures are also affecting the remote montane-boreal lakes on the SE Tibetan Plateau, fossil pollen and diatom data from two lakes were synthesized. The interplay of aquatic and terrestrial ecosystem response was explored in respect to climate variability and human activity over the past 200 years. Nonmetric multidimensional scaling and Procrustes rotation analysis were undertaken to determine whether pollen and diatom responses in each lake were similar and synchronous. Detrended canonical correspondence analysis was used to develop quantitative estimates of compositional species turnover. Despite instrumental evidence of significant climatic warming on the southeastern Plateau, the pollen and diatom records indicate very stable species composition throughout their profiles and show only very subtle responses to environmental changes over the past 200 years. The compositional species turnover (0.36-0.94 SD) is relatively low in comparison to the species reorganizations known from the periods during the mid-and early-Holocene (0.64-1.61 SD) on the SE Plateau, and also in comparison to turnover rates of sediment records from climate-sensitive regions in the circum arctic. Our results indicate that climatically induced ecological thresholds are not yet crossed, but that human activity has an increasing influence, particularly on the terrestrial ecosystem in our study area. Synergistic processes of post-Little Ice Age warming, 20th century climate warming and extensive reforestations since the 19th century have initiated a change from natural oak-pine forests to seminatural, likely less resilient pine-oak forests. Further warming and anthropogenic disturbances would possibly exceed the ecological threshold of these ecosystems and lead to severe ecological consequences.
In this work, the adsorption and splitting of the water molecule by light and/or an external potential is investigated in the frame of (photo-) electrochemical cells using a rutile ruthenium dioxide anode. With the help of periodic density functional calculations, the adsorbed structures of H(2)O and some radicals involved in the splitting process (O, OH, OOH) are obtained and compared with the available experimental results. On the basis of these electronic-structure calculations, we use a method to calculate the stability of the reaction intermediates and conclude on the thermodynamical possibility of the water splitting reaction at the surface. We demonstrate that a moderate overpotential of 0.64 V is required for the reaction to take place at the RuO(2)(110) surface.
Substantial investment in climate change research has led to dire predictions of the impacts and risks to biodiversity. The Intergovernmental Panel on Climate Change fourth assessment report(1) cites 28,586 studies demonstrating significant biological changes in terrestrial systems(2). Already high extinction rates, driven primarily by habitat loss, are predicted to increase under climate change(3-6). Yet there is little specific advice or precedent in the literature to guide climate adaptation investment for conserving biodiversity within realistic economic constraints(7). Here we present a systematic ecological and economic analysis of a climate adaptation problem in one of the world's most species-rich and threatened ecosystems: the South African fynbos. We discover a counterintuitive optimal investment strategy that switches twice between options as the available adaptation budget increases. We demonstrate that optimal investment is nonlinearly dependent on available resources, making the choice of how much to invest as important as determining where to invest and what actions to take. Our study emphasizes the importance of a sound analytical framework for prioritizing adaptation investments(4). Integrating ecological predictions in an economic decision framework will help support complex choices between adaptation options under severe uncertainty. Our prioritization method can be applied at any scale to minimize species loss and to evaluate the robustness of decisions to uncertainty about key assumptions.
We present the Potsdam Parallel Ice Sheet Model (PISM-PIK), developed at the Potsdam Institute for Climate Impact Research to be used for simulations of large-scale ice sheet-shelf systems. It is derived from the Parallel Ice Sheet Model (Bueler and Brown, 2009). Velocities are calculated by superposition of two shallow stress balance approximations within the entire ice covered region: the shallow ice approximation (SIA) is dominant in grounded regions and accounts for shear deformation parallel to the geoid. The plug-flow type shallow shelf approximation (SSA) dominates the velocity field in ice shelf regions and serves as a basal sliding velocity in grounded regions. Ice streams can be identified diagnostically as regions with a significant contribution of membrane stresses to the local momentum balance. All lateral boundaries in PISM-PIK are free to evolve, including the grounding line and ice fronts. Ice shelf margins in particular are modeled using Neumann boundary conditions for the SSA equations, reflecting a hydrostatic stress imbalance along the vertical calving face. The ice front position is modeled using a subgrid-scale representation of calving front motion (Albrecht et al., 2011) and a physically-motivated calving law based on horizontal spreading rates. The model is tested in experiments from the Marine Ice Sheet Model Intercomparison Project (MISMIP). A dynamic equilibrium simulation of Antarctica under present-day conditions is presented in Martin et al. (2011).
Using Milky Way data of the new Effelsberg-Bonn HI Survey (EBHIS) and the Galactic All-Sky Survey (GASS), we present a revised picture of the high-velocity cloud (HVC) complex Galactic center negative (GCN). Owing to the higher angular resolution of these surveys compared to previous studies (e.g., the Leiden Dwingeloo Survey), we resolve complex GCN into lots of individual tiny clumps, that mostly have relatively broad line widths of more than 15 km s(-1). We do not detect a diffuse extended counterpart, which is unusual for an HVC complex. In total 243 clumps were identified and parameterized which allows us to statistically analyze the data. Cold-line components (i.e.,Delta upsilon(fwhm) < 7.5 km s(-1)) are found in about 5% only of the identified cloudlets. Our analysis reveals that complex GCN is likely built up of several subpopulations that do not share a common origin. Furthermore, complex GCN might be a prime example for warm-gas accretion onto the Milky Way, where neutral HI clouds are not stable against interaction with the Milky Way gas halo and become ionized prior to accretion.
The cell nucleus harbors a large number of proteins involved in transcription, RNA processing, chromatin remodeling, nuclear signaling, and ribosome assembly. The nuclear genome of the model alga Chlamydomonas reinhardtii P. A. Dang. was recently sequenced, and many genes encoding nuclear proteins, including transcription factors and transcription regulators, have been identified through computational discovery tools. However, elucidating the specific biological roles of nuclear proteins will require support from biochemical and proteomics data. Cellular preparations with enriched nuclei are important to assist in such analyses. Here, we describe a simple protocol for the isolation of nuclei from Chlamydomonas, based on a commercially available kit. The modifications done in the original protocol mainly include alterations of the differential centrifugation parameters and detergent-based cell lysis. The nuclei-enriched fractions obtained with the optimized protocol show low contamination with mitochondrial and plastid proteins. The protocol can be concluded within only 3 h, and the proteins extracted can be used for gel-based and non-gel-based proteomic approaches.
The Guarguaraz Complex in West Argentina formed during collision between the microplate Chilenia and South America. It is composed of neritic clastic metasediments with intercalations of metabasic and ultrabasic rocks of oceanic origin. Prograde garnet growth in metapelite and metabasite occurred between 1.2 GPa, 470 degrees C and 1.4 GPa, 530 degrees C, when the penetrative s(2)-foliation was formed. The average age of garnet crystallization of 390 +/- 2 Ma (2 sigma) was determined from three four-point Lu-Hf mineral isochrones from metapelite and metabasite samples and represents the time of collision. Peak pressure conditions are followed by a decompression path with slight heating at 0.5 GPa, 560 degrees C. Fluid release during decompression caused equilibration of mineral compositions at the rims and also aided Ar diffusion. An Ar-40/39 Ar plateau age of white mica at 353 +/- 1 Ma (1 sigma) indicates the time of cooling below 350-400 degrees C. These temperatures were attained at pressures of 0.2-0.3 GPa, indicative of an average exhumation rate of >= 1 mm/a for the period 390-353 Ma. Late hydrous influx at 0.1-0.3 GPa caused pervasive growth of sericite and chlorite and reset the Ar/Ar ages of earlier coarse-grained white mica. At 284-295 Ma, the entire basement cooled below 280 degrees C (fission track ages of zircon) after abundant post-collisional granitoid intrusion. The deeply buried epicontinental sedimentary rocks, the high peak pressure referring to a low metamorphic geotherm of 10-12 degrees C/km, and the decompression/heating path are characteristics of material buried and exhumed within a (micro) continent-continent collisional setting.
The meadow grasshopper, Chorthippus parallelus (Zetterstedt), is common and widespread in Central Europe, with a low dispersal range per generation. A population study in Central Germany (Frankenwald and Thuringer Schiefergebirge) showed strong interpopulation differences in abundance and individual fitness. We examined genetic variability using microsatellite markers within and between 22 populations in a short-to long-distance sampling (19 populations, Frankenwald, Schiefergebirge, as well as a southern transect), and in the Erzgebirge region (three populations), with the latter aiming to check for effects as a result of historical forest cover. Of the 671 C. parallelus captured, none was macropterous (functionally winged). All populations showed a high level of expected and observed heterozygosity (mean 0.80-0.90 and 0.60-0.75, respectively), whereas there was evidence of inbreeding (F(IS) values all positive). Allelic richness for all locus-population combinations was high (mean 9.3-11.2), whereas alleles per locus ranged from 15-62. At a local level, genic and genotypic differences were significant. Pairwise F(ST) values were in the range 0.00-0.04, indicating little interpopulation genetic differentiation. Similarly, the calculated gene flow was very high, based on the respective F(ST) (19.5) and using private alleles (7.7). A Neighbour-joining tree using Nei's D(A) and principal coordinate analysis separated two populations that were collected in the Erzgebirge region. Populations from this region may have escaped the effects of the historical forest cover. The visualization of the spatial arrangement of genotypes revealed one geographical barrier to gene flow in the short-distance sampling.
This paper discusses a hitherto undescribed usage of the particle so as a dedicated focus marker in contemporary German. I discuss grammatical and pragmatic characteristics of this focus marker, supporting my account with natural linguistic data and with controlled experimental evidence showing that so has a significant influence on speakers' understanding of what the focus expression in a sentence is. Against this background, I sketch a possible pragmaticalization path from referential usages of so via hedging to a semantically bleached focus marker, which, unlike particles such as auch 'also'/'too' or nur 'only', does not contribute any additional meaning.
Challenges in understanding the hydrologic controls on the mobility of slow-moving landslides
(2011)
Slow-moving landslides are a wide-spread type of active mass movement, can cause severe damages to infrastructure, and may be a precursor of sudden catastrophic slope failures. Pore-water pressure is commonly regarded as the most important among a number of possible factors controlling landslide velocity. We used high-resolution monitoring data to explore the relations of landslide mobility and hydrologic processes at the Heumoser landslide in Austria, which is characterized by continuous slow movement along a shear zone. Movement rates showed a seasonality that was associated with elevated pore-water pressures. Pore pressure monitoring revealed a system of confined and separated aquifers with differing dynamics. Analysis of a simple infinite slope mobility model showed that small variations in parameters, along with measured pore pressure dynamics, provided a perfect match to our observations. Modeling showed a stabilizing effect of snow cover due to the additional load. This finding was supported by a multiple regression model, which further suggested that effective pore pressures at the slip surface were partially differing from the borehole observations and were related to preferential infiltration and subsurface flow in adjacent areas. It appears that in a setting like the Heumoser landslide, hydrologic processes delicately influence slope mobility through their control on pore pressure dynamics and the weight of the landslide body, which challenges observation and modeling. Moreover, it appears that their simplicity, and especially their high sensitivity to parameter variations, limits the conclusions that can be drawn from infinite slope models.
A common problem in ecology is identifying the relationship between relief and site properties obtainable only by point measurements. The method of Multi-Scale Landscape Analysis (MSLA) identifies such correlations. MSLA combines frequency filtering of the digital elevation model (DEM) with an estimation of the optimum filter coefficients using an optimization procedure. Tested using point data of soil decarbonation from a German young moraine landscape, MSLA provided significant results. Implemented within open source software SAMT. MSLA is comfortable and flexible to use, offering applications for numerous other spatial analysis problems.
This study monitors regional changes in the crystallinity of carbonaceous matter (CM) by applying Micro-Raman spectroscopy to a total of 214 metasediment samples (largely so-called Bundnerschiefer) dominantly metamorphosed under blueschist- to amphibolite-facies conditions. They were collected within the northeastern margin of the Lepontine dome and easterly adjacent areas of the Swiss Central Alps. Three-dimensional mapping of isotemperature contours in map and profile views shows that the isotemperature contours associated with the Miocene Barrow-type Lepontine metamorphic event cut across refolded nappe contacts, both along and across strike within the northeastern margin of the Lepontine dome and adjacent areas. Further to the northeast, the isotemperature contours reflect temperatures reached during the Late Eocene subduction-related blueschist-facies event and/or during subsequent near-isothermal decompression; these contours appear folded by younger, large-scale post-nappe-stacking folds. A substantial jump in the recorded maximum temperatures across the tectonic contact between the frontal Adula nappe complex and surrounding metasediments indicates that this contact accommodated differential tectonic movement of the Adula nappe with respect to the enveloping Bundnerschiefer after maximum temperatures were reached within the northern Adula nappe, i.e. after Late Eocene time.
Vorwort
(2011)
A new class of fluorescent dyes based on 1,3-benzodioxole and [1,3]-dioxolo[4.5-f]benzodioxole
(2011)
We report on synthesis and photophysical properties of a new class of fluorescent dyes. They are characterized by large Stokes-shifts, long fluorescence lifetimes in organic solvents and a pronounced dependency of the fluorescence lifetime on the solvent polarity. Also worthy of note is the high bleaching stability. To provide access to biochemical and medical applications a series of derivatives were prepared, which exhibit specific reactivity towards different biologically relevant functional groups (carboxylic acids, amines, maleimides, N-hydroxysuccinimide esters). Furthermore, two alkynes were prepared, which could be used in 'Click' chemistry.
A new concept of a stereoselective synthesis of axially chiral biaryls, formed in the course of the dehydro-Diels-Alder (DDA) reaction, has been disclosed. It is based on asymmetric induction of the newly formed chirality axis by a chirality center, which is present in the two synthesized DDA reactants. Depending on the different length of the linkers joining the alkyne moieties the DDA reaction may be triggered photochemically or thermally, where only the thermal variant was stereoselective.
Five alkynyl pyridines were prepared and cyclized to naphthylpyridines as the main products in the course of a Photo-Dehydro-Diels-Alder reaction. Four of the final products are axially chiral and the determination of the rotational barrier by DFT calculations, dynamic NMR and H PLC experiments is demonstrated. (C) 2011 Elsevier B.V. All rights reserved.
The photo-dehydro-Diels-Alder (PDDA) reaction is a valuable extension of the classical Diels-Alder (DA) reaction. The PDDA reaction differs from the DA reaction by the replacement of one of the C-C-double bonds of the diene moiety by a C-C triple bond and by the photochemical triggering of the reaction. This entails that, in contrast to the DA reaction, the PDDA reaction proceeds according to a multistage mechanism with biradicals and cycloallenes as intermediates. The PDDA reaction provides access to a considerable variety of compound classes. For example, 1-phenylnaphthlenes, 1,1'-binaphthyls, N-heterocyclic biaryls, and naphthalenophanes could be obtained by this reaction.
Preparation of Strained Axially Chiral (1,5)Naphthalenophanes by Photo-dehydro-Diels-Alder Reaction
(2011)
The preparation of 10 (1,5)naphthalenophanes (10a-j) by photo-dehydro-Diels-Alder (PDDA) reaction is described. Owing to hindered rotation around the biaryl axis, compounds 10 are axially chiral and the separation of enantiomers by chiral HPLC was demonstrated in three cases (10a,b,e). The absolute configuration of the isolated enantiomers could be unambiguously determined by comparison of calculated and measured circular dichroism (CD) spectra. Furthermore, we analyzed ring strain phenomena of (1,5)naphthalenophanes 10. Depending on the length of the linker units, one can distinguish three classes of naphthalenophanes. Compounds 10a-c are highly strained (E-STR = 7-31 kcal/mol), and the strain is caused by small bond angles in the linker unit and deformation of the naphthalene moiety. Another type of strain is observed if the linker unit becomes relatively long (10g,h) originating from transannular interactions and is comparable with the well-known strain of medium sized rings. The naphthalenophanes 10d-f with a linker length of 10-14 atoms are only marginally strained. To clearly discriminate the different sources of strain, we defined two geometrical parameters (average central dihedral angle delta(C) and naphthalene thickness D-N) and demonstrated that they are well-suited to indicate naphthalene deformation of our naphthalenophanes 10 as well as of ten model naphthalenophanes (I-X) with different linker lengths and linking positions.
This article deals with the claim that the MAGNITUDE ESTIMATION (ME) method of gathering acceptability judgments produces data that are more informative for linguists than binary or n-point scale judgments. We performed three acceptability-rating experiments that directly compared ME data to binary and seven-point scale data. The results clearly falsify the hypothesis that data gathered by the ME method carry a larger amount of information about the acceptability of a given linguistic phenomenon. The three measures are largely equivalent with respect to informativity. Moreover, ME judgments are shown to be more liable to producing spurious variance under certain circumstances.*
Objectives: Stroke, frequently a consequence of hypertension, is one of the leading causes of death and neurological disabilities worldwide. In the ischemic brain, levels of endothelin-1, one of the most potent vasoconstrictors, are raised. Anti-inflammatory and neuroprotective effects of endothelin antagonists after stroke have been described in literature. Based on these findings, we investigated the protective effect of the endothelin converting enzyme/neutral endopeptidase blocker, SLV 338, in salt-loaded, stroke-prone, spontaneously hypertensive rats.
Methods: Male, 8-week-old spontaneously hypertensive stroke-prone rats were put on a high salt diet and treated with either 30 mg/kg or 100 mg/kg SLV 338 or vehicle for 27 weeks. Blood pressure, neurological outcome, body weight, and mortality were investigated throughout treatment. In weeks 1 and 9, animals were housed in metabolic cages for collection of urinary and blood samples and assessment of salt water and food intake. In weeks 22 and 27, additional blood samples were taken. At the end of the study, all brains were analyzed using magnetic resonance imaging.
Results: SLV 338 was well tolerated in all animals. Neurological outcome and infarct size were similar in all groups. Albuminuria was considerably delayed and the incidence of stroke significantly lowered in treated animals. In spontaneously hypertensive stroke-prone rats, treatment with SLV 338 significantly (P=0.01) improved survival in comparison to the vehicle treated group in a blood pressure-independent manner.
Discussion: Our data in spontaneously hypertensive stroke-prone rats demonstrate that combined endothelin converting enzyme/neutral endopeptidase inhibition could offer a new therapeutic approach for primary stroke prevention and improvement of mortality. The mechanism seems to be blood pressure-independent.
Der Aufsatz zeigt, dass es sich bei der averroischen Bearbeitung der aristotelischen ‚Poetik‘ um eine in sich konsistente Theorie der Dichtung handelt, die allerdings mit der aristotelischen Konzeption der Dichtung nur wenig zu tun hat. Ausgehend von der Übersetzung von ‚Tragödie‘ und ‚Komödie‘ mit ‚Lob‘ und ‚Tadel‘ entwickelt Averroes einen Begriff von Dichtung als moralphilosophisches Argument zum Lob der Tugend und zum Tadel des Lasters. Im Mittelpunkt steht die Interpretation des aristotelischen Begriffs der mimesis als similitudo, das heißt als Gleichnis. Als gleichnishaftes Argument ist Dichtung nur graduell von anderen argumentativen Formen wie der demonstrativen Logik und der Rhetorik unterschieden.
Der Aufsatz umreißt die Wirkung von Averroes’ Bearbeitung der aristotelischen ‚Poetik‘ als argumentativer Disziplin. Beginnend mit Al-Farabi und Al-Gazali im zehnten Jahrhundert wird die ‚Poetik‘ den logischen Disziplinen des ‚Organon‘ zugerechnet. Während die Theorie eines ‚poetischen Syllogismus‘ nicht rezipiert worden ist, wurde der argumentative Status der Dichtung vom zwölften Jahrhundert an auch im lateinischen Westen bekannt. Mit unterschiedlichen Begründungen übernahmen Dominicus Gundissalinus, Vincenz von Beauvais, Albertus Magnus, Roger Bacon und Thomas von Aquin die Klassifizierung der Poetik als argumentative Disziplin. Am Ende des Aufsatzes steht ein Ausblick auf Coluccio Salutatis ‚De laboribus Herculis‘ und die humanistische Rezeption dieser Tradition.
The enzyme diisopropyl fluorophosphatase (DFPase) from the squid Loligo vulgaris is of great interest because of its ability to catalyze the hydrolysis of highly toxic organophosphates. In this work, the enzyme structure in solution (native state) was studied by use of different scattering methods. The results are compared with those from hydrodynamic model calculations based on the DFPase crystal structure. Bicontinuous microemulsions made of sugar surfactants are discussed as host systems for the DFPase. The microemulsion remains stable in the presence of the enzyme, which is shown by means of scattering experiments. Moreover, activity assays reveal that the DFPase still has high activity in this complex reaction medium. To complement the scattering experiments cryo-SEM was also employed to study the microemulsion structure.