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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.
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.
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.
We have measured differential cross sections (DCSs) for the reaction H + D-2 -> HD- (v' = 2, j' = 0,3,6,9) + D at center-of-mass collision energies E-coll of 1.25, 1.61, and 1.97 eV using the photoloc technique. The DCSs show a strong dependence on the product rotational quantum number. For the HD(v' = 2, j' = 0) product, the DCS is bimodal but becomes oscillatory as the collision energy is increased. For the other product states, they are dominated by a single peak, which shifts from back to sideward scattering as j' increases, and they are in general less sensitive to changes in the collision energy. The experimental results are compared to quantum mechanical calculations and show good, but not fully quantitative agreement.
Cavitation at the solid surface normally begins with nucleation, in which defects or assembled molecules located at a liquid-solid interface act as nucleation centers and are actively involved in the evolution of cavitation bubbles. Here, we propose a simple approach to evaluate the behavior of cavitation bubbles formed under high intensity ultrasound (20 kHz, 51.3 W cm (2)) at solid surfaces, based on sonication of patterned substrates with a small roughness (less than 3 nm) and controllable surface energy. A mixture of octadecylphosphonic acid (ODTA) and octadecanethiol (ODT) was stamped on the Si wafer coated with different thicknesses of an aluminium layer (20-500 nm). We investigated the growth mechanism of cavitation bubble nuclei and the evolution of individual pits (defects) formed under sonication on the modified surface. A new activation behavior as a function of Al thickness, sonication time, ultrasonic power and temperature is reported. In this process cooperativity is introduced, as initially formed pits further reduce the energy to form bubbles. Furthermore, cavitation on the patterns is a controllable process, where up to 40-50 min of sonication time only the hydrophobic areas are active nucleation sites. This study provides a convincing proof of our theoretical approach on nucleation.
The circular dichroism (CD) induced by femtosecond laser pulse excitation of 3-methylcyclopentanone has been investigated by means of experiment and theory as a function of the laser pulse duration. In the experiment the CD in ion yields is measured by femtosecond laser ionization via a one-photon resonant excited state. In the theoretical part the CD is calculated by solving laser driven quantum electron dynamics for the same resonant excitation based on ab initio electronic structure calculations employing a complete description of the electric field-electric dipole and magnetic field-magnetic dipole interactions. Both the experimentally measured CD in ion yields and the calculated CD in excited state populations exhibit a marked increase of the CD for pulse duration increasing from 50 fs to about 200 fs. Beyond 200 fs pulse duration the CD levels off. The combination of experimental and theoretical evidences indicates that the CD decreases with increasing laser intensity connected to the increased coupling between the excited states.
Integrated real-time visualisation of massive 3D-Point clouds and geo-referenced textured dates
(2011)
Understanding changes in biodiversity in agricultural landscapes in relation to land-use type and intensity is a major issue in current ecological research. In this context nutrient enrichment has been identified as a key mechanism inducing species loss in Central European grassland ecosystems. At the same time, insights into the linkage between agricultural land use and plant nutrient status are largely missing. So far, studies on the relationship between chemical composition of plant community biomass and biodiversity have mainly been restricted to wetlands and all these studies neglected the effects of land use. Therefore, we analyzed aboveground biomass of 145 grassland plots covering a gradient of land-use intensities in three regions across Germany. In particular, we explored relationships between vascular plant species richness and nutrient concentrations as well as fibre contents (neutral and acid detergent fibre and lignin) in the aboveground community biomass.
We found the concentrations of several nutrients in the biomass to be closely linked to plant species richness and land use. Whereas phosphorus concentrations increased with land-use intensity and decreased with plant species richness, nitrogen and potassium concentrations showed less clear patterns. Fibre fractions were negatively related to nutrient concentrations in biomass, but hardly to land-use measures and species richness. Only high lignin contents were positively associated with species richness of grasslands. The N:P ratio was strongly positively related to species richness and even more so to the number of endangered plant species, indicating a higher persistence of endangered species under P (co-)limited conditions. Therefore, we stress the importance of low P supply for species-rich grasslands and suggest the N:P ratio in community biomass to be a useful proxy of the conservation value of agriculturally used grasslands.
Trait-based studies have become extremely common in plant ecology. Trait-based approaches often rely on the tacit assumption that intraspecific trait variability (ITV) is negligible compared to interspecific variability, so that species can be characterized by mean trait values. Yet, numerous recent studies have challenged this assumption by showing that ITV significantly affects various ecological processes. Accounting for ITV may thus strengthen trait-based approaches, but measuring trait values on a large number of individuals per species and site is not feasible. Therefore, it is important and timely to synthesize existing knowledge on ITV in order to (1) decide critically when ITV should be considered, and (2) establish methods for incorporating this variability. Here we propose a practical set of rules to identify circumstances under which ITV should be accounted for. We formulate a spatial trait variance partitioning hypothesis to highlight the spatial scales at which ITV cannot be ignored in ecological studies. We then refine a set of four consecutive questions on the research question, the spatial scale, the sampling design, and the type of studied traits, to determine case-by-case if a given study should quantify ITV and test its effects. We review methods for quantifying ITV and develop a step-by-step guideline to design and interpret simulation studies that test for the importance of ITV. Even in the absence of quantitative knowledge on ITV, its effects can be assessed by varying trait values within species within realistic bounds around the known mean values. We finish with a discussion of future requirements to further incorporate ITV within trait-based approaches. This paper thus delineates a general framework to account for ITV and suggests a direction towards a more quantitative trait-based ecology.
The article compares the postdemocracy with the postsocialism. At first the paper analyzes the debate of the postdemocracy and points out an analytical model of postdemocracy. Afterwards the paper searches for symptoms of the postdemocracy within the case of Russia which appears as one possible ideal type of postsocialism. The comparison shows that both post-phenomenons are two sides of one global process of transformation. However, the case of postsocialism acts as a trendsetter. The postsocialist Russia sets an example for the possible developments of the postdemocracy.
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.
The inversion of the flexible five-membered ring in tetrahydrodicyclopentadiene (TH-DCPD) derivatives remains fast on the NMR timescale even at 103 K. Since the intramolecular exchange process could not be sufficiently slowed for spectroscopic evaluation, the conformational equilibrium is thus inaccessible by dynamic NMR. Fortunately, the spatial magnetic properties of the aryl and carbonyl groups attached to the DCPD skeleton can be employed in order to evaluate the conformational state of the system. In this context, the anisotropic effects of the functional groups in the H-1 NMR spectra prove to be the molecular response property of spatial nucleus independent chemical shifts (NICS).
Understanding and predicting the composition and spatial structure of communities is a central challenge in ecology. An important structural property of animal communities is the distribution of individual home ranges. Home range formation is controlled by resource heterogeneity, the physiology and behaviour of individual animals, and their intra- and interspecific interactions. However, a quantitative mechanistic understanding of how home range formation influences community composition is still lacking. To explore the link between home range formation and community composition in heterogeneous landscapes we combine allometric relationships for physiological properties with an algorithm that selects optimal home ranges given locomotion costs, resource depletion and competition in a spatially-explicit individual-based modelling framework. From a spatial distribution of resources and an input distribution of animal body mass, our model predicts the size and location of individual home ranges as well as the individual size distribution (ISD) in an animal community. For a broad range of body mass input distributions, including empirical body mass distributions of North American and Australian mammals, our model predictions agree with independent data on the body mass scaling of home range size and individual abundance in terrestrial mammals. Model predictions are also robust against variation in habitat productivity and landscape heterogeneity. The combination of allometric relationships for locomotion costs and resource needs with resource competition in an optimal foraging framework enables us to scale from individual properties to the structure of animal communities in heterogeneous landscapes. The proposed spatially-explicit modelling concept not only allows for detailed investigation of landscape effects on animal communities, but also provides novel insights into the mechanisms by which resource competition in space shapes animal communities.
Standing stocks are typically easier to measure than process rates such as production. Hence, stocks are often used as indicators of ecosystem functions although the latter are generally more strongly related to rates than to stocks. The regulation of stocks and rates and thus their variability over time may differ, as stocks constitute the net result of production and losses. Based on long-term high frequency measurements in a large, deep lake we explore the variability patterns in primary and bacterial production and relate them to those of the corresponding standing stocks, i.e. chlorophyll concentration, phytoplankton and bacterial biomass. We employ different methods (coefficient of variation, spline fitting and spectral analysis) which complement each other for assessing the variability present in the plankton data, at different temporal scales. In phytoplankton, we found that the overall variability of primary production is dominated by fluctuations at low frequencies, such as the annual, whereas in stocks and chlorophyll in particular, higher frequencies contribute substantially to the overall variance. This suggests that using standing stocks instead of rate measures leads to an under- or overestimation of food shortage for consumers during distinct periods of the year. The range of annual variation in bacterial production is 8 times greater than biomass, showing that the variability of bacterial activity (e.g. oxygen consumption, remineralisation) would be underestimated if biomass is used. The P/B ratios were variable and although clear trends are present in both bacteria and phytoplankton, no systematic relationship between stock and rate measures were found for the two groups. Hence, standing stock and process rate measures exhibit different variability patterns and care is needed when interpreting the mechanisms and implications of the variability encountered.
The analysis of palaeoclimate time series is usually affected by severe methodological problems, resulting primarily from non-equidistant sampling and uncertain age models. As an alternative to existing methods of time series analysis, in this paper we argue that the statistical properties of recurrence networks - a recently developed approach - are promising candidates for characterising the system's nonlinear dynamics and quantifying structural changes in its reconstructed phase space as time evolves. In a first order approximation, the results of recurrence network analysis are invariant to changes in the age model and are not directly affected by non-equidistant sampling of the data. Specifically, we investigate the behaviour of recurrence network measures for both paradigmatic model systems with non-stationary parameters and four marine records of long-term palaeoclimate variations. We show that the obtained results are qualitatively robust under changes of the relevant parameters of our method, including detrending, size of the running window used for analysis, and embedding delay. We demonstrate that recurrence network analysis is able to detect relevant regime shifts in synthetic data as well as in problematic geoscientific time series. This suggests its application as a general exploratory tool of time series analysis complementing existing methods.
The aim of this paper is to estimate the Hurst parameter of Fractional Gaussian Noise (FGN) using Bayesian inference. We propose an estimation technique that takes into account the full correlation structure of this process. Instead of using the integrated time series and then applying an estimator for its Hurst exponent, we propose to use the noise signal directly. As an application we analyze the time series of the Nile River, where we find a posterior distribution which is compatible with previous findings. In addition, our technique provides natural error bars for the Hurst exponent.
To gain a deeper understanding of the mechanisms behind biomass accumulation, it is important to study plant growth behavior. Manually phenotyping large sets of plants requires important human resources and expertise and is typically not feasible for detection of weak growth phenotypes. Here, we established an automated growth phenotyping pipeline for Arabidopsis thaliana to aid researchers in comparing growth behaviors of different genotypes.
The analysis pipeline includes automated image analysis of two-dimensional digital plant images and evaluation of manually annotated information of growth stages. It employs linear mixed-effects models to quantify genotype effects on total rosette area and relative leaf growth rate (RLGR) and ANOVAs to quantify effects on developmental times.
Using the system, a single researcher can phenotype up to 7000 plants d(-1). Technical variance is very low (typically < 2%). We show quantitative results for the growth-impaired starch-excessmutant sex4-3 and the growth-enhancedmutant grf9.
We show that recordings of environmental and developmental variables reduce noise levels in the phenotyping datasets significantly and that careful examination of predictor variables (such as d after sowing or germination) is crucial to avoid exaggerations of recorded phenotypes and thus biased conclusions.