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Im Auftrag des Staates
(2011)
Folter ist ein Akt extremer kollektiver Gewalt, der im Auftrag eines Staates im Geheimen ausgeübt wird. Die Frage, was Menschen dazu bringt, anderen Menschen diese extreme Gewalt anzutun, verengt den Blick für ein Verständnis der Folter allzu schnell auf individualistische Erklärungsversuche. Der vorliegende Aufsatz geht im Gegensatz dazu von der Gruppe der Folterer aus und rückt die sozialen Beziehungen dieser Form der Vergesellschaftung und die von ihnen ausgehenden sozialen Dynamiken und Effekte in den Mittelpunkt. In einem ersten Schritt werden Georg Simmels formale Bestimmungen der geheimen Gesellschaft rekonstruiert und auf die geheime Gesellschaft der Folterer angewandt und spezifiziert; auf dieser Grundlage werden im zweiten Schritt Handlungsbedingungen der Mitglieder der geheimen Gesellschaft der Folterer herausgearbeitet; der dritte Schritt bestimmt die eigendynamischen Prozesse des Phänomens der Folter, die aus der Eskalation politischer Konflikte, der Gruppe der Folterer und der Situation der Folter erwachsen. Die These lautet, dass sich aus der Perspektive einer relationalen Soziologie ein theoretischer Zugriff auf das Problem der Folter ergibt, der weiterführende Erklärungen des Phänomens ermöglicht.
Sobre los orígenes y la evaluación de los Germanos en la literatura alemana de los siglos XVI
(2011)
Los conceptos que tenían los habitantes del Sacro Imperio Romano sobre la nación germana respecto a su filiación étnica y sus orígenes cambian a partir del inicio de la historia moderna. A través del análisis de los ejemplos más relevantes el presente estudio traza las líneas maestras de este proceso de apropiación e interpretción del pasado que empieza con la recepción de la Germania de Tácito por los escritores humanistas y se prolonga a lo largo de los siglos XVII, XVIII y XIX.
Moderne Bürgerreligion
(2011)
Das Reckahner Besucherbuch
(2011)
Der Bürger entscheidet mit
(2011)
»Warum erregt der geplante Abriss eines Bahnhofs die Nation, während gegen das hundertfache Sterben von Bibliotheken immer nur ein paar Stimmen laut werden? Wo sind die Wutbürger, wenn man sie braucht?«, überlegte sich hierzulande Tilman Spreckelsen.1 Die Kernfrage lautet also: Stehen die Bürger eigentlich hinter der Bibliothek? Ob und wie die Bürgerschaft für ihre Öffentliche Bibliothek entscheidet, wenn sie entscheiden darf, wird im vorliegenden Aufsatz thematisiert. Ergebnisse von Bürgerbegehren und Bürgerentscheiden stehen dabei im Fokus, da bürgerschaftliches Engagement bei diesen Mitwirkungsinstrumenten besonders gefragt ist und es gleichzeitig kommunalpolitische Folgen haben kann. Am Beispiel von Stuttgart 21 wird darüber hinaus der Fragestellung nachgegangen, wie sich eine Öffentliche Bibliothek zu Sachverhalten positioniert, die (nicht nur) kommunalpolitisch brisant sind.
Mehr Chancen als Risiken
(2011)
Anne Christensen spricht von partizipativer Entwicklung, wenn sie sich zum Komplex Bibliothek 2.0 äußert, und meint damit primär die stärkere Einbeziehung der Benutzer, wenn es um die Zukunft der kollaborativen Erschließung von Medien in Bibliothekskatalogen geht.1 Diese Art der Partizipation tangiert Kernaufgaben sowohl an Öffentlichen als auch an wissenschaftlichen Bibliotheken. Über die Beteiligung der Benutzer am Katalog 2.0 hinaus könnte auch durch eine weitere Form der Partizipation Einfl uss auf die Zukunft Öffentlicher Bibliotheken genommen werden: durch den Bürgerhaushalt.
Mindfulness and acceptance describe the skills necessary to experience emotions and thoughts (e.g., performance-interfering cognitions) consciously and without judging them. This article introduces the mindfulness and acceptance approach and its potential in the context of competitive sports. Definitions as well as research results related to mechanisms of action and differential psychological aspects are given and the efficacy of the approach in the field of clinical psychology is reviewed. The rationale and implementation of the mindfulness-acceptance-commitment approach, an approach adapted for performance enhancement, is illustrated. Finally, evidence from psychotherapy research is presented, and a recommendation for the use of mindfulness and acceptance in the context of competitive sports is given.
Spielberger's (1972) Trait-State-Anxiety theory distinguishes between anxiety as a trait (A-trait) - involving a stable characteristic of a person to react with anxiety in response to varying situations and anxiety as a state (A-state), a situation-dependent reaction to a stimulus perceived as threatening. Using a general instead of a sport-specific measure, a previous study provided only mixed support for core predictions of the theory as related to sports (Schwenkmezger, 1985). With the aid of enhanced instruments and statistical methods, we tested these predictions again. The multidimensional and competition-specific assessment of anxiety results in support for the assumption of a stable A-trait and a fluctuating A-state, whereby the A-trait not only predicts the intensity of A-states but also the A-state variability. The repeated assessment of A-states prior to two competitions reveals a rather low relative consistency (i.e., interindividual differences across measurements were only moderately stable). Especially this latter finding suggests that, in order to gain a full understanding of the experience of competitive anxiety in athletes, sport psychologists should not only assess competitive A-traits, but also repeatedly measure competitive A-states.
The present article analyzes the socio-economic background of maths teachers in Germany and its relation to career-related decisions and job-related convictions. These analyzes is based on data collected through questionnaires answered by 1126 maths teachers working at a sample of secondary schools representative of Germany. Following Bourdieu's theory, the authors examine whether the economic and cultural conditions prevailing in the teachers' families of origin are related to their decision to pursue this specific professional career or to their job-related convictions. Furthermore, it is analyzed in how far teachers, in their everyday work in the classroom, meet students from groups of origin foreign to the teachers themselves. The results show that the teachers, socio-economic background has no systematic relation to either their career-related decisions or their job-related convictions.
The present study examines whether the use of different frequency scales in questionnaires about physical activity influences respondents' own estimation of their activity, as well as subsequent measurements of health- und sport-related cognitions and evaluations. Using a randomized research design we recruited a sample of 118 participants. One group received a high frequency scale for assessing their exercise frequency with the response categories "never", "less often", "once a month", "once a week", or "most days." The other group answered with a medium frequency scale with the alternatives "never", "less often", " once every few months", "once a month", and " once a week or more often." As dependent variables all participants judged the subjective importance of physical activity and their health-related quality of life (WHO-QOL-bref). Results indicate the expected response errors, owing to the fact that using a high-frequency scale produces higher levels of self-reported physical activity (Cramer's V = .30). Corresponding to this the subjective importance of physical activity increased (d = .37) and the health-related quality of life was judged to be better (d = .36). Such artefacts might be eliminated by using standardized formulations such as "I exercise... times per week/month for... minutes."
Signals from the past forms and functions of the traditional behavior in Thomas Kling's essay
(2011)
The link between pornography use, normative acceptance of sexual aggression, and the presence of risk factors of sexual aggression in sexual scripts for consensual sexual interactions was studied in a sample of 197 adolescents in Germany. Risk factors included sex after only a short acquaintanceship, alcohol and drug use in sexual interactions, and ambiguous communication of sexual intentions. In addition to a measure of overall pornography use, exposure to portrayals of consensual sex, coerced sex and degrading sex was measured. Almost all participants had seen pornografic material at least once, just under half had seen depictions of coerced sex. Significant correlations were found between all measures of pornography use and the presence of risk factors of sexual aggression in consensual sexual scripts. Violent pornography usage showed a positive correlation with the normative acceptance of sexual aggression that was partly accounted for by sexual scripts. The findings are discussed with regard to the significance of pornografic media contents in the process of adolescents' sexual socialization.
Previous studies on the electoral fortunes of extreme right parties (ERPs) have pointed to the importance of variables of party competition for the success - or failure - of ERPs. These studies vary greatly when it comes to describing the political opportunity structure of the extreme right. Apart from their methodological differences, existing studies differ especially with regard to the assumed underlying dimension of party competition. This article tests the impact of three frequently discussed variables in the political opportunity structure of ERPs (mainstream party convergence, position of the established right and party system polarisation) on the vote share of ERPs in Western Europe. In addition to examining previous studies in this field, it focuses on the interplay between the economic and the cultural dimensions as part of the political opportunity structure. The authors show that a decrease in polarisation with regard to economic questions is accompanied by a growing salience of ERPs' core issues, leading in the end to an increase in ERPs' vote share.
The Karaburun Peninsula, which is considered part of the Anatolide-Tauride Block of Turkey, contains clastic and carbonate sequences deposited on the northern margin of Gondwana. The Palaeozoic clastic sequence, which is intruded by the Early Triassic granitoid and tectonically overlies a Mesozoic melange sequence, can be divided into three subunits: a lower clastic subunit consisting of a sandstone-shale alternation, an upper clastic subunit consisting of black chert-bearing shales, sandstone and conglomerate, and a Permo-Carboniferous carbonate subunit. The lower Triassic Karaburun I-type granitoid has a high initial Sr-87/Sr-86 ratio (0.709021-0.709168), and low Nd-143/Nd-144 ratio (0.512004-0.512023) and epsilon Nd (-5.34 to -5.70) isotopic values. Geochronological data indicate a crystallization (intrusion) age of 247.1 +/- 2.0 Ma (Scythian). Geochemically, the acidic magmatism reflects a subduction-related continental-arc basin tectonic setting, which can be linked to the opening of the northern branch of Neo-Tethys as a continental back-arc rifting basin on the northern margin of Gondwana. This can be related to the closure through southward subduction of the Palaeotethys Ocean beneath Gondwana.
Cross-coupling reactions, such as Buchwald-Hartwig arylamination and direct intramolecular biaryl coupling by C-H activation, were carried out using various Palladium-N-heterocyclic carbenes (Pd-NHC) as catalysts. The yields were good to excellent. The latter strategy was adopted to transform two dibenzylbutane lignans, isolated from the leaves of Ocotea macrophylla (Lauraceae), into the corresponding dibenzocyclooctane lignans in good overall yields. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications (R) to view the free supplemental file.
Random matrix theory (RMT) is well suited to describing the emergent properties of systems with complex interactions amongst their constituents through their eigenvalue spectrums. Some RMT results are applied to the problem of clustering high dimensional biological data with complex dependence structure amongst the variables. It will be shown that a gene relevance or correlation network can be constructed by choosing a correlation threshold in a principled way, such that it corresponds to a block diagonal structure in the correlation matrix, if such a structure exists. The structure is then found using community detection algorithms, but with parameter choice guided by RMT predictions. The resulting clustering is compared to a variety of hierarchical clustering outputs and is found to the most generalised result, in that it captures all the features found by the other considered methods.
Phase behaviour and the mesoscopic structure of zwitanionic surfactant mixtures based on the zwitterionic tetradecyldimethylamine oxide (TDMAO) and anionic lithium perfluoroalkyl carboxylates have been investigated for various chain lengths of the perfluoro surfactant with an emphasis on spontaneously forming vesicles. These mixtures were studied at a constant total concentration of 50 mM and characterised by means of dynamic light scattering (DLS), electric conductivity, small-angle neutron scattering (SANS), viscosity, and cryo-scanning electron microscopy (Cryo-SEM). No vesicles are formed for relatively short perfluoro surfactants. The extension of the vesicle phase becomes substantially larger with increasing chain length of the perfluoro surfactant, while at the same time the size of these vesicles increases. Head group interactions in these systems play a central role in the ability to form vesicles, as already protonating 10 mol% of the TDMAO largely enhances the propensity for vesicle formation. The range of vesicle formation in the phase diagram is not only substantially enlarged but also extends to shorter perfluoro surfactants, where without protonation no vesicles would be formed. The size and polydispersity of the vesicles are related to the chain length of the perfluoro surfactant, the vesicles becoming smaller and more monodisperse with increasing perfluoro surfactant chain length. The ability of the mixed systems to form well-defined unilamellar vesicles accordingly can be controlled by the length of the alkyl chain of the perfluorinated surfactant and depends strongly on the charge conditions, which can be tuned easily by pH-variation.
Diffusion in a series of ionic liquids is investigated by a combination of Broadband Dielectric Spectroscopy (BDS) and Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). It is demonstrated that the mean jump lengths increase with the molecular volumes determined from quantum-chemical calculations. This provides a direct means-via Einstein-Smoluchowski relation-to determine the diffusion coefficient by BDS over more than 8 decades unambiguously and in quantitative agreement with PFG NMR measurements. New possibilities in the study of charge transport and dynamic glass transition in ionic liquids are thus opened.
A set of double thermoresponsive diblock copolymers poly(N-n-propylacrylamide)-block-poly(N-ethylacrylamide) (PNPAM-b-PNEAM) was synthesised by sequential reversible addition-fragmentation chain transfer (RAFT) polymerisations. Using a twofold trimethylsilyl (TMS)-labeled RAFT-agent, the relative size of the two blocks was varied. While soluble as unimers below 15 degrees C, all copolymers exhibited thermally induced two-step self-assembly in water, due to distinct lower critical solution temperature (LCST) phase transitions of PNPAM (around 20 degrees C) and PNEAM (around 70 degrees C). Their temperature-dependent self-organisation in dilute aqueous solution was studied by turbidimetry, dynamic light scattering, transmission electron microscopy, and (1)H NMR spectroscopy. The copolymers show distinct, two-step self-organisation behaviour with respect to transition temperatures, aggregate type and size, which can be correlated to the relative lengths of the low and high LCST blocks. For polymers having short blocks with low LCST, the first thermal transition induces the formation of individual micelles. Further heating above the second thermal transition results reversibly either in a shrink of the micelle size or in aggregation of the micelles, with hydrodynamic diameters below 250 nm. In contrast in the case of polymers having a long block with low LCST, the first thermal transition already leads to clusters of micelles, while the second thermal transition makes the clusters shrink. Noteworthy, the twofold TMS-labeled end groups report not only on the molar masses of the polymers, but can simultaneously serve as NMR-probes for the self-assembly process. The signal of the TMS-aryl end group displays a reversible temperature dependent, two-step splitting that is indicative of the self-organisation of the block copolymers.
Soft, physically crosslinking, block copolymer elastomers were filled with surface-treated nanoparticles, in order to evaluate the possibility for improvement of their properties when used as soft dielectric actuators. The nanoparticles led to improvements in dielectric properties, however they also reinforced the elastomer matrix. Comparing dielectric spectra of composites with untreated and surface-treated particles showed a measurable influence of the surface on the dielectric loss behaviour for high filler amounts, strongly indicating an improved host-guest interaction for the surface-treated particles. Breakdown strength was measured using a test bench and was found to be in good agreement with the results from the actuation measurements. Actuation responses predicted by a model for prestrained actuators agreed well with measurements up to a filler amount of 20%(vol). Strong improvements in actuation behaviour were observed, with an optimum near 15%(vol) nanoparticles, corresponding to a reduction in electrical field of 27% for identical actuation strains. The use of physically crosslinking elastomer ensured the mechanical properties of the matrix elastomer were unchanged by nanoparticles effecting the crosslinking reaction, contrary to similar experiments performed with chemically crosslinking elastomers. This allows for a firm conclusion about the positive effects of surface-treated nanoparticles on actuation behavior.
The formation of secondary Ln(III) solid phases (e.g. Nd(OH)CO3 and Sm(OH)CO3) has been studied as a function of the humic acid (HA) concentration in 0.1 M NaClO4 aqueous solution and their solubility has been investigated in the neutral pH range (6.5-8) under normal atmospheric conditions. Nd(III) and Sm(III) were selected as analogues for trivalent lanthanide and actinide ions. The solid phases under investigation have been prepared by alkaline precipitation and characterized by TGA, ATR-FTIR, XRD, TRLFS, DR-UV-Vis and Raman spectroscopy, and solubility measurements. The spectroscopic data obtained indicate that Nd(OH)CO3 and Sm(OH)CO3 are stable and remain the solubility limiting solid phases even in the presence of increased HA concentration (0.5 g/L) in solution. Upon base addition in the Ln(III)-HA system decomplexation of the previously formed Ln(III)-humate complexes and precipitation of two distinct phases occurs, the inorganic (Ln(OH)CO3) and the organic phase (HA), which is adsorbed on the particle surface of the former. Nevertheless, HA affects the particle size of the solid phases. Increasing HA concentration results in decreasing crystallite size of the Nd(OH)CO3 and increasing crystallite size of the Sm(OH)CO3 solid phase, and affects inversely the solubility of the solid phases. However, this impact on the solid phase properties is expected to be of minor relevance regarding the chemical behavior and migration of trivalent lanthanides and actinides in the geosphere.
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.
Can you see me in the snow? - action simulation aids the detection of visually degraded human motion
(2011)
Using a novel paradigm, we demonstrate that action simulation can directly facilitate ongoing perception of people's movements. Point-light actors (PLAs) representing common human motions were shown embedded in a visual noise reminiscent of "TV snow". At first, the PLAs were perceived clearly, then occluded from view for a short duration, during which it was hypothesized that a real-time action simulation was generated tracking the motion's course. The PLA then reappeared in motion at variable visibility against the noise, whilst detection thresholds for the reappearance were measured. In the crucial manipulation, the test motion was either temporally congruent with the motion as it would have continued during occlusion, and thus temporally matching the simulation, or temporally incongruent. Detection thresholds were lower for congruent than for incongruent reappearing motions, suggesting that reappearing motion that temporally matched the internal action simulation was more likely to be detected.
The lexical database dlexDB supplies in form of an online database frequency-based norms of numerous process-related word properties for psychological and linguistic research. These values include well known variables such as printed frequency of word form and lemma as documented also in CELEX (Baayen, Piepenbrock und Gulikers, 1995). In addition, we compute new values like frequencies based on syllables, and morphemes as well as frequencies of character chains, and multiple word combinations. The statistics are based on the Kernkorpus des Digitalen Wrterbuchs der deutschen Sprache (DWDS) with over 100 million running words. We illustrate the validity of these norms with new results about fixation durations in sentence reading.
The present study investigates diagnostic skills of German teachers in estimating basic reading capacities of sixth graders and the way they relate to achievement heterogeneity of the judged student group and to students' language background.
The data were obtained from a sample of 39 German teachers and their classes in the context of the Berlin Longitudinal Reading Study. Judgements on different levels were analysed (achievement of sixth graders in general and of individual students). Diagnostic skills were investigated using different indicators: the personal judgement error and tendency and the accuracy in identifying achievement differences between individual students (rank component). The accuracy in estimating reading capacities of students with and without a different language background was investigated by means of achievement level matched pairs.
The outcomes indicated, among others, an overestimation of students' general achievement level and on average an acceptable accuracy in identifying achievement differences between individual students. They showed equal difficulties in judging performances of students with and without a different language background.
Yeast hexokinase isoenzyme ScHxk2 stability of a two-domain protein with discontinuous domains
(2011)
The hexokinase isoenzyme 2 of Saccharomyces cerevisiae (ScHxk2) represents an archetype of a two-domain protein with the active site located in a cleft between the two domains. Binding of the substrate glucose results in a rigid body movement of the two domains leading to a cleft closure of the active site. Both domains of this enzyme are composed of discontinuous peptide sequences. This structural feature is reflected in the stability and folding of the ScHxk2 protein. Structural transitions induced by urea treatment resulted in the population of a thermodynamically stable folding intermediate, which, however, does not correspond to a molecule with one domain folded and the other unfolded. As demonstrated by different spectroscopic techniques, both domains are structurally affected by the partial denaturation. The intermediate possesses only 40% of the native secondary structural content and a substantial increase in the Stokes radius as judged by circular dichroism and dynamic light scattering analyses. One-dimensional H-1 NMR data prove that all tryptophan residues are in a non-native environment in the intermediate, indicating substantial changes in the tertiary structure. Still, the intermediate possesses quite a high stability for a transition intermediate of about Delta G = -22 kJ mol(-1).
As part of the POPS study (Potsdam prevention of eating disorders) 300 adolescents aged between 10 and 13 years completed questionnaires measuring satisfaction with weight and muscles, body change strategies and disturbed eating behavior. More than half of the girls and a third of the boys are dissatisfied with their weight. Nearly 70% of the male participants were unhappy with their muscles. Both forms of body dissatisfaction are influenced by similar sociocultural and psychological factors. While weight dissatisfaction leads to weight reduction strategies and disturbed eating, muscle dissatisfaction results in muscle enhancement methods. Potential harmful consequences of excessive muscle building techniques are discussed. The data emphasize the need for a sex-specific investigation of body dissatisfaction and its consequences. Body image aspects relevant to boys should be added to intervention and prevention approaches.
Past research indicates an association in adults and young people of emotional and contextual factors with a higher risk for the development of eating disorders or obesity. Few studies focus on problematic eating patterns in childhood, especially in association with parental feeding strategies. 482 mothers completed a questionnaire about eating behaviors and the weight status of their 1- to 10-year-old child as well as their own feeding strategies. A classification of the child's eating behavior (food responsiveness, emotional eating, external eating, eating time and meal structure) using hierarchical cluster analysis revealed a conspicuous eating pattern (10 %) showing above-average values in all eating behaviors. Controlling for weight and demographic variables mothers of children with conspicuous eating patterns were characterized by restrictive strategies and were less likely to encourage or facilitate their child to control his or her eating. Similar problematic eating patterns were also identified in early childhood. The association of maternal feeding strategies - beyond weight control issues - with conspicuous eating patterns in children might indicate a possibility of early prevention through parent training.
A thermosensitive statistical copolymer based on oligo(ethylene glycol) methacrylates incorporating biotin was synthesized by free radical copolymerisation. The influence of added avidin on its thermoresponsive behaviour was investigated. The specific binding of avidin to the biotinylated copolymers provoked a marked increase of the lower critical solution temperature.
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.
The molecular mechanisms of animal cell osmoregulation are poorly understood. Genetic studies of osmoregulation in yeast have identified mucin-like proteins as critical regulators of osmosensitive signaling and gene expression. Whether mucins play similar roles in higher organisms is not known. Here, we show that mutations in the Caenorhabditis elegans mucin-like gene osm-8 specifically disrupt osmoregulatory physiological processes. In osm-8 mutants, normal physiological responses to hypertonic stress, such as the accumulation of organic osmolytes and activation of osmoresponsive gene expression, are constitutively activated. As a result, osm-8 mutants exhibit resistance to normally lethal levels of hypertonic stress and have an osmotic stress resistance (Osr) phenotype. To identify genes required for Osm-8 phenotypes, we performed a genome-wide RNAi osm-8 suppressor screen. After screening,18,000 gene knockdowns, we identified 27 suppressors that specifically affect the constitutive osmosensitive gene expression and Osr phenotypes of osm-8 mutants. We found that one suppressor, the transmembrane protein PTR-23, is co-expressed with osm-8 in the hypodermis and strongly suppresses several Osm-8 phenotypes, including the transcriptional activation of many osmosensitive mRNAs, constitutive glycerol accumulation, and osmotic stress resistance. Our studies are the first to show that an extracellular mucin-like protein plays an important role in animal osmoregulation in a manner that requires the activity of a novel transmembrane protein. Given that mucins and transmembrane proteins play similar roles in yeast osmoregulation, our findings suggest a possible evolutionarily conserved role for the mucin-plasma membrane interface in eukaryotic osmoregulation.
Characterizing the local site response in large cities is an important step towards seismic hazard assessment. To this regard, single station seismic noise measurements were carried out at 146 sites in the northern part of Santiago de Chile. This extensive survey allowed the fundamental resonance frequency of the sedimentary cover, derived from horizontal-to-vertical (H/V) spectral ratios, to be mapped. By inverting the spectral ratios under the constraint of the thickness of the sedimentary cover, known from previous gravimetric measurements, local S-wave velocity profiles have been retrieved. After interpolation between the individual profiles, the resulting high resolution 3D S-wave velocity model allows the entire area, as well as deeper parts of the basin, to be represented in great detail. Since one lithology shows a great scatter in the velocity values only a very general correlation between S-wave velocity in the uppermost 30 m (v(s)(30)) and local geology is found. Local S-wave velocity profiles can serve as a key factor in seismic hazard assessment, since they allow an estimate of the amplification potential of the sedimentary cover. Mapping the intensity distribution of the 27 February 2010 Maule, Chile, event (Mw = 8.8) the results indicate that local amplification of the ground motion might partially explain the damage distribution and encourage the use of the low cost seismic noise techniques for the study of seismic site effects.
Based on the analysis of optical absorption spectra, it has recently been speculated that the excitonic coupling between individual azobenzene-functionalized alkanethiols arranged in a self-assembled monolayer (SAM) on a gold surface could be strong enough to hinder collective trans-cis isomerization-on top of steric hindrance [Gahl et al., J. Am. Chem. Soc., 2010, 132, 1831]. Using models of SAMs of increasing complexity (dimer, linear N-mers, and two-dimensionally arranged N-mers) and density functional theory on the (TD-) B3LYP/6-31G* level, we determine optical absorption spectra, the nature and magnitude of excitonic couplings, and the corresponding spectral shifts. It is found that at inter-monomer distances of about 20 angstrom and above, TD-B3LYP excitation frequencies (and signal intensities) can be well described by the frequently used point-dipole approximation. Further, calculated blue shifts in optical absorption spectra account for the experimental observations made for azobenzene/gold SAMs, and hint to the fact that they can indeed be responsible for reduced switching probability in densely packed self-assembled structures.
The spatial magnetic properties (through space NMR shieldings-TSNMRS) of metal complexes (with ligands such as acetylacetone, 3-hydroxy-pyran(4) one) and "metallobenzenes" have been calculated by the GIAO perturbation method and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various sizes and directions. The TSNMRS values, thus obtained, can be successfully employed to quantify and visualize partial aromaticity of the metallocyclic ring by comparison with the spatial magnetic properties of the corresponding non-complexed ligands in comparable structural and electronic situations, and benzene, respectively. Because anisotropy/ring current effects in H-1 NMR spectra proved to be the molecular response property of TSNMRS, the results obtained concerning partial "chelatoaromaticity" are experimentally ensured.
Pure and europium (Eu3+) doped cerium dioxide (CeO2) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of similar to 250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce4+ sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 degrees C, a remarkable high surface area of similar to 120 m(2) g (-1) is preserved whereas an enrichment of the surface Ce4+ relative to Ce3+ ions and relative strong europium emission with a lifetime of similar to 1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.
The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C4Py](2)[CuCl4] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl4](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl4](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.
Using scattering scanning nearfield infrared microscopy (s-SNIM), we have imaged the nanoscale phase separation of mixed polystyrene-poly(methyl methacrylate) (PS-PMMA) brushes and investigated changes in the top layer as a function of solvent exposure. We deduce that the top-layer of the mixed brushes is composed primarily of PMMA after exposure to acetone, while after exposure to toluene this changes to PS. Access to simultaneously measured topographic and chemical information allows direct correlation of the chemical morphology of the sample with topographic information. Our results demonstrate the potential of s-SNIM for chemical mapping based on distinct infrared absorption properties of polymers with a high spatial resolution of 80 nm x 80 nm.
This study addresses the effect of ionic strength and type of ions on the structure and water content of polyelectrolyte multilayers. Polyelectrolyte multilayers of poly(sodium-4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium chloride) (PDADMAC) prepared at different NaF, NaCl and NaBr concentrations have been investigated by neutron reflectometry against vacuum, H2O and D2O. Both thickness and water content of the multilayers increase with increasing ionic strength and increasing ion size. Two types of water were identified, "void water" which fills the voids of the multilayers and does not contribute to swelling but to a change in scattering length density and "swelling water" which directly contributes to swelling of the multilayers. The amount of void water decreases with increasing salt concentration and anion radius while the amount of swelling water increases with salt concentration and anion radius. This is interpreted as a denser structure in the dry state and larger ability to swell in water (sponge) for multilayers prepared from high ionic strengths and/or salt solution of large anions. No exchange of hydration water or replacement of H by D was detected even after eight hours incubation time in water of opposing isotopic composition.
An electronic friction approach based on Langevin dynamics is used to describe the multidimensional (six-dimensional) dynamics of femtosecond laser induced desorption of H-2 and D-2 from a H(D)-covered Ru(0001) surface. The paper extends previous reduced-dimensional models, using a similar approach. In the present treatment forces and frictional coefficients are calculated from periodic density functional theory (DFT) and essentially parameter-free, while the action of femtosecond laser pulses on the metal surface is treated by using the two-temperature model. Our calculations shed light on the performance and validity of various adiabatic, non-adiabatic, and Arrhenius/Kramers type kinetic models to describe hot-electron mediated photoreactions at metal surfaces. The multidimensional frictional dynamics are able to reproduce and explain known experimental facts, such as strong isotope effects, scaling of properties with laser fluence, and non-equipartitioning of vibrational, rotational, and translational energies of desorbing species. Further, detailed predictions regarding translations are made, and the question for the controllability of photoreactions at surfaces with the help of vibrational preexcitation is addressed.