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Self-assembly phenomena in block copolymer systems are attracting considerable interest from the scientific community and industry alike. Particularly interesting is the behavior of amphiphilic copolymers, which can self-organize into nanoscale-sized objects such as micelles, vesicles, or tubes in solution, and which form well-defined assemblies at interfaces such as air-liquid, air-solid, or liquid-solid. Depending on the polymer chemistry and architecture, various types of organization at interfaces can be expected, and further exploited for applications in nanotechnology, electronics, and biomedical sciences.
In this article, we discuss the formation and characterization of Langmuir monolayers from various amphiphilic block copolymers, including chargeable and thus pH-responsivematerials. Solid-supported polymer films are reviewed in the context of alteration of surface properties by ultrathin polymer layers and the possibilities for application in tissue engineering, sensors and biomaterials. Finally, we focus on how organic and polymer monolayers influence the growth of inorganic materials. This is a truly biomimetic approach since Nature uses soft interfaces to control the nucleation, growth, and morphology of biominerals such as calcium phosphate, calcium carbonate, and silica.
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).
Efficacy of Psychotherapy with Children and Adolescents
Psychotherapeutic interventions require empirical as well as scientific assessment. Specifically, the proven efficacy of psychotherapy for children and adolescents is essential. Thus, studies examining treatment efficacy and meta-analyses are necessary to compare effect sizes of individual therapeutic interventions between treatment groups and waiting control groups. Assessment of 138 primary studies from 1993-2009 documented the efficacy of psychotherapy for children and adolescents. Furthermore, behavioural therapy outperformed non-behavioural interventions, as 90 % of behavioural interventions showed larger effect sizes compared to non-behavioural psychotherapy. Analysis of moderator variables demonstrated an improved treatment efficacy for individual therapy, inclusion of the family, treatment of internalised disorders, and in clinical samples. Stability of psychotherapeutic treatment effects over time was demonstrated.
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.