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Quantum chemical approach to atomic manipulation of chlorobenzene on the Si(111)-7 x 7 surface
(2017)
We present a cluster model to describe the localization of hot charge carriers on the Si(111)-7 x 7 surface, which leads to (nonlocal) desorption of chlorobenzene molecules in scanning tunneling microscope (STM) manipulation experiments. The localized charge carriers are modeled by a small cluster. By means of quantum chemical calculations, this cluster model explains many experimental findings from STM manipulation. We show that the negative charge is mainly localized in the surface, while the positive one also resides on the molecule. Both resonances boost desorption: In the negative resonance the adatom is elevated; in the positive one the chemisorption bond between the silicon surface adatom and chlorobenzene is broken. We find normal modes promoting desorption matching experimental low-temperature activation energies for electron-and hole-induced desorption.
The mechanism of the primary ammonium/tertiary amine-mediated ring-opening polymerization of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) was investigated. Kinetic analyses revealed that the normal amine mechanism (NAM) together with a dormant-active chain end equilibrium were responsible for the controlled nature of this polymerization pathway, but that the polymerization also proceeded via the activated monomer mechanism (AMM). Mixtures of primary amines (1 equiv) and tertiary amines (0-1.5 equiv) were therefore tested to confirm the co-existence of the NAM and AMM and determine the limits for a controlled polymerization. For tertiary amine molar fractions smaller than 0.8 equiv, the reaction times were greatly reduced (compared to primary amine-initiated polymerization) without compromising the control of the reaction. Hence, the polymerization of NCA can proceed in a controlled manner even when the AMM contributes to the overall chain growth mechanism. (C) 2017 Elsevier Ltd. All rights reserved.
X-ray Bragg diffraction in sagittal geometry on a Y-cut langasite crystal (La3Ga5SiO14) modulated by Lambda = 3 mu m Rayleigh surface acoustic waves was studied at the BESSY II synchrotron radiation facility. Owing to the crystal lattice modulation by the surface acoustic wave diffraction, satellites appear. Their intensity and angular separation depend on the amplitude and wavelength of the ultrasonic superlattice. Experimental results are compared with the corresponding theoretical model that exploits the kinematical diffraction theory. This experiment shows that the propagation of the surface acoustic waves creates a dynamical diffraction grating on the crystal surface, and this can be used for space-time modulation of an X-ray beam.
An interesting feature of solar wind fluctuations is the occasional presence of a well-pronounced peak near the spectral knee. These peaks are well investigated in the context of magnetic field fluctuations in the magnetosheath and they are typically related to kinetic plasma instabilities. Recently, similar peaks were observed in the spectrum of ion flux fluctuations of the solar wind and magnetosheath. In this paper, we propose a simple analytical model to describe such peaks in the ion flux spectrum based on the linear theory of plasma fluctuations. We compare our predictions with a sample observation in the solar wind. For the given observation, the peak requires similar to 10 minutes to grow up to the observed level that agrees with the quasi-linear relaxation time. Moreover, our model well reproduces the form of the measured peak in the ion flux spectrum. The observed lifetime of the peak is about 50 minutes, which is relatively close to the nonlinear Landau damping time of 30-40 minutes. Overall, our model proposes a plausible scenario explaining the observation.
Islands are ideal systems to model temporal changes in biodiversity and reveal the influence of humans on natural communities. Although theory predicts biodiversity on islands tends towards an equilibrium value, the recent extinction of large proportions of island biotas complicates testing this model. The well-preserved subfossil record of Caribbean bats-involving multiple insular radiations-provides a rare opportunity to model diversity dynamics in an insular community. Here, we reconstruct the diversity trajectory in noctilionoid bats of the Greater Antilles by applying a dynamic model of colonization, extinction and speciation to phylogenetic and palaeontological data including all known extinct and extant species. We show species richness asymptotes to an equilibrium value, a demonstration of natural equilibrium dynamics across an entire community. However, recent extinctions-many caused by humans-have wiped out nearly a third of island lineages, dragging diversity away from equilibrium. Using a metric to measure island biodiversity loss, we estimate it will take at least eight million years to regain pre-human diversity levels. Our integrative approach reveals how anthropogenic extinctions can drastically alter the natural trajectory of biological communities, resulting in evolutionary disequilibrium.
Chytrids are a diverse group of ubiquitous true zoosporic fungi. The recent molecular discovery of a large diversity of undescribed chytrids has raised awareness on their important, but so far understudied ecological role in aquatic ecosystems. In the pelagic zone, of both freshwater and marine ecosystems, many chytrid species have been morphologically described as parasites on almost all major groups of phytoplankton. However, the majority of these parasitic chytrids has rarely been isolated and lack DNA sequence data, resulting in a large proportion of "dark taxa" in databases. Here, we report on the isolation and in-depth morphological, molecular and host range characterization of a chytrid infecting the common freshwater desmid Staurastrum sp. We provide first insights on the metabolic activity of the different chytrid development stages by using the vital dye FUN (R)-1 (2-chloro-4-[2,3-dihydro-3-methyl-[benzo-1,3-thiazol-2-yl]-methylidene]-1-phenylquinolinium iodide). Cross infection experiments suggest that this chytrid is an obligate parasite and specific for the genus Staurastrum sp. Phylogenetic analysis, based on ITS1-5.8S-ITS2 and 28S rDNA sequences, placed it in the order Rhizophydiales. Based on the unique zoospore ultrastructure, combined with thallus morphology, and molecular phylogenetic placement, we describe this parasitic chytrid as a new genus and species Staurastromyces oculus, within a new family Staurastromycetaceae. (C) 2017 Elsevier GmbH. All rights reserved.
Erosion processes, aggravated by human activity, have a large impact on the spatial variation of soil and topographic properties. Knowledge of the topography prior to human-induced erosion (paleotopography) in naturally stable landscapes is valuable for identifying vulnerable landscape positions and is required as starting point for erosion modelling exercises. However, developing accurate reconstructions of paleotopography provide a major challenge for geomorphologists. Here, we present a set of paleotopographies for a closed kettle hole catchment in north-east Germany (4 ha), obtained through different reconstruction approaches. Current soil and colluvium thickness, estimated from a dataset of 264 soil descriptions using Ordinary Kriging, were used as input for a mass balance, or were compared with a set of undisturbed soil thicknesses to estimate the amount of erosion. The performance of the different approaches was assessed with cross-validation and the count of mispredicted eroded, depositional or stable landscape positions. The paleotopographic reconstruction approach based on the average thickness of undisturbed soils in the study area showed the best performance. This thickness (1.00 m) is comparable to the average undisturbed soil thickness in the region and in line with global correlations of soil thickness as a function of rainfall and initial CaCO3 content. The performance of the different approaches depended more on mispredictions of landscape position due to the assumption of a spatially constant initial soil depth than on small variations in this depth. To conclude, we mention several methodological and practical points of attention for future topography reconstruction studies, concerning data quality and availability, spatial configuration of data and other processes affecting topography. (C) 2017 Elsevier B.V. All rights reserved.
Disentangling eco-evolutionary dynamics of predator-prey coevolution: the case of antiphase cycles
(2017)
The impact of rapid predator-prey coevolution on predator-prey dynamics remains poorly understood, as previous modelling studies have given rise to contradictory conclusions and predictions. Interpreting and reconciling these contradictions has been challenging due to the inherent complexity of model dynamics, defying mathematical analysis and mechanistic understanding. We develop a new approach here, based on the Geber method for deconstructing eco-evolutionary dynamics, for gaining such understanding. We apply this approach to a co-evolutionary predator-prey model to disentangle the processes leading to either antiphase or 1/4-lag cycles. Our analysis reveals how the predator-prey phase relationship is driven by the temporal synchronization between prey biomass and defense dynamics. We further show when and how prey biomass and trait dynamics become synchronized, resulting in antiphase cycles, allowing us to explain and reconcile previous modelling and empirical predictions. The successful application of our proposed approach provides an important step towards a comprehensive theory on eco-evolutionary feedbacks in predator-prey systems.
Absorption Tails of Donor
(2017)
In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D A complexes occur at photon energies below the optical gaps of both the donors and the C-60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C-60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes.
In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems.
Recent event-related potential (ERP) data showed that neutral objects encoded in emotional background pictures were better remembered than objects encoded in neutral contexts, when recognition memory was tested one week later. In the present study, we investigated whether this long-term memory advantage for items is also associated with correct memory for contextual source details. Furthermore, we were interested in the possibly dissociable contribution of familiarity and recollection processes (using a Remember/Know procedure). The results revealed that item memory performance was mainly driven by the subjective experience of familiarity, irrespective of whether the objects were previously encoded in emotional or neutral contexts. Correct source memory for the associated background picture, however, was driven by recollection and enhanced when the content was emotional. In ERPs, correctly recognized old objects evoked frontal ERP Old/New effects (300-500 ms), irrespective of context category. As in our previous study (Ventura-Bort et al., 2016b), retrieval for objects from emotional contexts was associated with larger parietal Old/New differences (600-800 ms), indicating stronger involvement of recollection. Thus, the results suggest a stronger contribution of recollection-based retrieval to item and contextual background source memory for neutral information associated with an emotional event.
Fast radio bursts (FRBs) are transient sources of unknown origin. Recent radio and optical observations have provided strong evidence for an extragalactic origin of the phenomenon and the precise localization of the repeating FRB 121102. Observations using the Karl G. Jansky Very Large Array (VLA) and very-long-baseline interferometry (VLBI) have revealed the existence of a continuum non-thermal radio source consistent with the location of the bursts in a dwarf galaxy. All these new data rule out several models that were previously proposed, and impose stringent constraints to new models. Aims. We aim to model FRB 121102 in light of the new observational results in the active galactic nucleus (AGN) scenario. Methods. We propose a model for repeating FRBs in which a non-steady relativistic e(+)-beam, accelerated by an impulsive magneto-hydrodynamic driven mechanism, interacts with a cloud at the centre of a star-forming dwarf galaxy. The interaction generates regions of high electrostatic field called cavitons in the plasma cloud. Turbulence is also produced in the beam. These processes, plus particle isotropization, the interaction scale, and light retardation effects, provide the necessary ingredients for short-lived, bright coherent radiation bursts. Results. The mechanism studied in this work explains the general properties of FRB 121102, and may also be applied to other repetitive FRBs. Conclusions. Coherent emission from electrons and positrons accelerated in cavitons provides a plausible explanation of FRBs.
Frailty and cardiac rehabilitation: A call to action from the EAPC Cardiac Rehabilitation Section
(2017)
Frailty is a geriatric syndrome characterised by a vulnerability status associated with declining function of multiple physiological systems and loss of physiological reserves. Two main models of frailty have been advanced: the phenotypic model (primary frailty) or deficits accumulation model (secondary frailty), and different instruments have been proposed and validated to measure frailty. However measured, frailty correlates to medical outcomes in the elderly, and has been shown to have prognostic value for patients in different clinical settings, such as in patients with coronary artery disease, after cardiac surgery or transvalvular aortic valve replacement, in patients with chronic heart failure or after left ventricular assist device implantation. The prevalence, clinical and prognostic relevance of frailty in a cardiac rehabilitation setting has not yet been well characterised, despite the increasing frequency of elderly patients in cardiac rehabilitation, where frailty is likely to influence the onset, type and intensity of the exercise training programme and the design of tailored rehabilitative interventions for these patients. Therefore, we need to start looking for frailty in elderly patients entering cardiac rehabilitation programmes and become more familiar with some of the tools to recognise and evaluate the severity of this condition. Furthermore, we need to better understand whether exercise-based cardiac rehabilitation may change the course and the prognosis of frailty in cardiovascular patients.
Am Abend des 29. Mai 2016 wurde der Ort Braunsbach im Landkreis Schwäbisch-Hall (Baden-Württemberg) von einer Sturzflut getroffen, bei der mehrere Häuser stark beschädigt oder zerstört wurden. Die Sturzflut war eine der Unwetterfolgen, die im Frühsommer 2016 vom Tiefdruckgebiet Elvira ausgelöst wurden. Der vorliegende Bericht ist der zweite Teil einer Doppelveröffentlichung, welche die Ergebnisse zur Untersuchung des Sturzflutereignisses im Rahmen des DFG-Graduiertenkollegs “Naturgefahren und Risiken in einer sich verändernden Welt” (NatRiskChange, GRK 2043/1) der Universität Potsdam präsentiert. Während Teil 1 die meteorologischen und hydrologischen Ereignisse analysiert, fokussiert Teil 2 auf die geomorphologischen Prozesse und die verursachten Gebäudeschäden. Dazu wurden Ursprung und Ausmaß des während des Sturzflutereignisses mobilisierten und in den Ort getragenen Materials untersucht. Des Weiteren wurden zu 96 betroffenen Gebäuden Daten zum Schadensgrad sowie Prozess- und Gebäudecharakteristika aufgenommen und ausgewertet. Die Untersuchungen zeigen, dass bei der Betrachtung von Hochwassergefährdung die Berücksichtigung von Sturzfluten und ihrer speziellen Charakteristika, wie hoher Feststofftransport und sprunghaftes Verhalten insbesondere in bebautem Gelände, wesentlich ist, um effektive Schutzmaßnahmen ergreifen zu können.
The Himalaya has a major influence on global and regional climate, in particular on the Asian monsoon system. The foreland basin of the Himalaya contains a record of tectonics and paleoclimate since the Miocene. Previous work on the evolution of vegetation and climate has focused on the central and western Himalaya, where a shift from C3 to C4 vegetation has been observed at similar to 7 Ma and linked to increased seasonality, but the climatic evolution of the eastern part of the orogen is less well understood. In order to track vegetation as a marker of monsoon intensity and seasonality, we analyzed delta C-13 and 8180 values of soil carbonate and associated delta C-13 values of bulk organic carbon from previously dated sedimentary sections exposing the syn-orogenic detrital Dharamsala and Siwalik Groups in the west, and, for the first time, the Siwalik Group in the east of the Himalayan foreland basin. Sedimentary records span from 20 to 1 Myr in the west (Joginder Nagar, Jawalamukhi, and Haripur Kolar sections) and from 13 to 1 Myr in the east (Kameng section), respectively. The presence of soil carbonate in the west and its absence in the east is a first indication of long-term lateral climatic variation, as soil carbonate requires seasonally arid conditions to develop. delta C-13 values in soil carbonate show a shift from around -10 parts per thousand to -2 parts per thousand at similar to 7 Ma in the west, which is confirmed by delta C-13 analyses on bulk organic carbon that show a shift from around -23 parts per thousand to -19 parts per thousand at the same time. Such a shift in isotopic values is likely to be associated with a change from C3 to C4 vegetation. In contrast, delta C-13 values of bulk organic carbon remain at 23 parts per thousand o in the east. Thus, our data show that the current east -west variation in climate was established at similar to 7 Ma. We propose that the regional change towards a more seasonal climate in the west is linked to a decrease of the influence of the Westerlies, delivering less winter precipitation to the western Himalaya, while the east remained annually humid due to its proximity to the monsoonal moisture source. (C) 2017 Elsevier B.V. All rights reserved.
In the era of the Internet of Things and Big Data modern cars have become mobile electronic systems or computers on wheels. Car sensors record a multitude of car and traffic related data as well as environmental parameters outside the vehicle. The data recorded are spatio-temporal by nature (floating car data) and can thus be classified as geodata. Their geospatial potential is, however, not fully exploited so far. In this paper, we present an approach to collect, process and visualize floating car data for traffic-and environment-related applications. It is demonstrated that cartographic visualization, in particular, is as effective means to make the enormous stocks of machine-recorded data available to human perception, exploration and analysis.
Dyskalkulie
(2017)
Hintergrund
Ausgeprägte Schwierigkeiten beim Erwerb der grundlegenden arithmetischen Fertigkeiten bei ansonsten durchschnittlichen Schulleistungen werden als Rechenstörung oder Dyskalkulie bezeichnet. Davon betroffen sind etwa 5 % der Grundschülerpopulation. Die Ursachen und die Symptome sind ebenso vielgestaltig wie die Methoden der differenziellen Förderung und Therapie.
Material und Methode
Selektive Literaturrecherche zur Rechenstörung aus verschiedenen mit dem Gegenstand befassten wissenschaftlichen Disziplinen.
Ergebnisse
Der Erwerb von Fähigkeiten zur Zahlenverarbeitung und zum Rechnen wird als ein erfahrungsabhängiger neuroplastischer Reifungsprozess verstanden, der zu einem komplexen, spezialisierten neuronalen Netzwerk führt und verschiedene kognitive Zahlenrepräsentationen hervorbringt. Die Entwicklung dieser domänenspezifischen Fähigkeiten ist abhängig von der Entwicklung domänenübergreifender Fähigkeiten, wie Aufmerksamkeit, Arbeitsgedächtnis, Sprache und visuell-räumlichen Fähigkeiten. Störungen dieser Reifungsprozesse können in verschiedenen Entwicklungsstadien unterschiedliche Komponenten der Entwicklung dieses komplexen kognitiven Systems betreffen und sind daher im klinischen Erscheinungsbild vielgestaltig. Sonderpädagogische, lerntherapeutische und ggf. medizinische Maßnahmen benötigen eine differenzielle Diagnostik und Indikationsstellung. Moderne computerbasierte Lernsoftware kann sowohl die schulische Didaktik als auch lerntherapeutische Vorgehensweisen unterstützen.
Schlussfolgerung
Frühzeitiges Erkennen sowie differenzielle und individualisierte Förderung können die Gefahr des Auftretens sekundärer emotionaler Störungen mindern. Die Diagnostik und die Behandlung der Rechenstörung sollten evidenzbasiert und leitlinienorientiert erfolgen sowie der Komplexität und Vielgestaltigkeit der Symptombildungen Rechnung tragen.
False positives and other statistical errors in standard analyses of eye movements in reading
(2017)
In research on eye movements in reading, it is common to analyze a number of canonical dependent measures to study how the effects of a manipulation unfold over time. Although this gives rise to the well-known multiple comparisons problem, i.e. an inflated probability that the null hypothesis is incorrectly rejected (Type I error), it is accepted standard practice not to apply any correction procedures. Instead, there appears to be a widespread belief that corrections are not necessary because the increase in false positives is too small to matter. To our knowledge, no formal argument has ever been presented to justify this assumption. Here, we report a computational investigation of this issue using Monte Carlo simulations. Our results show that, contrary to conventional wisdom, false positives are increased to unacceptable levels when no corrections are applied. Our simulations also show that counter-measures like the Bonferroni correction keep false positives in check while reducing statistical power only moderately. Hence, there is little reason why such corrections should not be made a standard requirement. Further, we discuss three statistical illusions that can arise when statistical power is low, and we show how power can be improved to prevent these illusions. In sum, our work renders a detailed picture of the various types of statistical errors than can occur in studies of reading behavior and we provide concrete guidance about how these errors can be avoided. (C) 2016 Elsevier Inc. All rights reserved.
Halloysites as tubular alumosilicates are introduced as inexpensive natural nanoparticles to form and stabilize oil-water emulsions. This stabilized emulsion is shown to enable efficient interfacial catalytic reactions. Yield, selectivity, and product separation can be tremendously enhanced, e.g., for the hydroformylation reaction of dodecene to tridecanal. In perspective, this type of formulation may be used for oil spill dispersions. The key elements of the described formulations are clay nanotubes (halloysites) which are highly anisometric, can be filled by helper molecules, and are abundantly available in thousands of tons, making this technology scalable for industrial applications.
Reduced expression of the Indy ("I am Not Dead, Yet") gene in lower organisms promotes longevity in a manner akin to caloric restriction. Deletion of the mammalian homolog of Indy (mIndy, Slc13a5) encoding for a plasma membrane-associated citrate transporter expressed highly in the liver, protects mice from high-fat diet-induced and aging-induced obesity and hepatic fat accumulation through a mechanism resembling caloric restriction. We studied a possible role of mIndy in human hepatic fat metabolism. In obese, insulin-resistant patients with nonalcoholic fatty liver disease, hepatic mIndy expression was increased and mIndy expression was also independently associated with hepatic steatosis. In nonhuman primates, a 2-year high-fat, high-sucrose diet increased hepatic mIndy expression. Liver microarray analysis showed that high mIndy expression was associated with pathways involved in hepatic lipid metabolism and immunological processes. Interleukin-6 (IL-6) was identified as a regulator of mIndy by binding to its cognate receptor. Studies in human primary hepatocytes confirmed that IL-6 markedly induced mIndy transcription through the IL-6 receptor and activation of the transcription factor signal transducer and activator of transcription 3, and a putative start site of the human mIndy promoter was determined. Activation of the IL-6-signal transducer and activator of transcription 3 pathway stimulated mIndy expression, enhanced cytoplasmic citrate influx, and augmented hepatic lipogenesis in vivo. In contrast, deletion of mIndy completely prevented the stimulating effect of IL-6 on citrate uptake and reduced hepatic lipogenesis. These data show that mIndy is increased in liver of obese humans and nonhuman primates with NALFD. Moreover, our data identify mIndy as a target gene of IL-6 and determine novel functions of IL-6 through mINDY. Conclusion: Targeting human mINDY may have therapeutic potential in obese patients with nonalcoholic fatty liver disease. German Clinical Trials Register: DRKS00005450.
Scenario-neutral response surfaces illustrate the sensitivity of a simulated natural system, represented by a specific impact variable, to systematic perturbations of climatic parameters. This type of approach has recently been developed as an alternative to top-down approaches for the assessment of climate change impacts. A major limitation of this approach is the underrepresentation of changes in the temporal structure of the climate input data (i.e., the seasonal and day-to-day variability) since this is not altered by the perturbation. This paper presents a framework that aims to examine this limitation by perturbing both observed and projected climate data time series for a future period, which both serve as input into a hydrological model (the HBV model). The resulting multiple response surfaces are compared at a common domain, the standardized runoff response surface (SRRS). We apply this approach in a case study catchment in Norway to (i) analyze possible changes in mean and extreme runoff and (ii) quantify the influence of changes in the temporal structure represented by 17 different climate input sets using linear mixed-effect models. Results suggest that climate change induced increases in mean and peak flow runoff and only small changes in low flow. They further suggest that the effect of the different temporal structures of the climate input data considerably affects low flows and floods (at least 21% influence), while it is negligible for mean runoff.
A substantial amount of research has revealed that cyberbully-victims have more emotional and behavioral problems than either cyberbullying victims or perpetrators. However, until now, little research has been conducted into the factors that contribute to the interplay between cyberbullying victimization and perpetration. The purpose of this study was to examine the relationship between cyberbullying victimization, perpetration, and two emotional components of alexithymia, namely difficulties in identifying and describing one's own feelings. Self-report questions were administered to 1549 adolescents between 12 and 18 years old (M = 14.51; SD = 1.68; 42.1% (n = 652) male) from Germany and Thailand. Results showed that cyberbullying victimization and alexithymia are associated with cyberbullying perpetration. Moreover, alexithymia mediated the associations between cyberbullying victimization and adolescents' cyberbullying perpetration. Consequently, we suggest that the ability to describe and identify one's own feelings might be important for understanding the link between cyberbullying, victimization, and perpetration. The results may help develop prevention and intervention programs focused on reducing cyberbullying.
The performance of organic photovoltaic blend devices is critically dependent on the polymer:fullerene interface. These interfaces are expected to impact the structural and thermal properties of the polymer with regards to the conjugated backbone planarity and transition temperatures during annealing/cooling processes. Here, we report the impact of fullerene intercalation on structural and thermal properties of poly(2,5-bis(3-tetradecylthiophen-2-yOthieno[3,2-b]thiophene (PBTTT), a highly stable material known to exhibit liquid crystalline behavior. We undertake a detailed systematic study of the extent of intercalation in the PBTTT:fullerene blend, considering the use of four different fullerene derivatives and also varying the loading ratios. Resonant Raman spectroscopy allows morphology in situ during controlled heating and cooling. We find that small fullerene molecules readily intercalate into PBTTT crystallites, resulting in a planarization of the polymer backbone, but high fullerene loading ratios or larger fullerenes result in nonintercalated domains. During cooling from melt, nonintercalated blend films are found to return to their original morphology and reproduce all thermal transitions on cooling with minimal hysteresis. Intercalated blend films show significant hysteresis on cooling due to the crystallized fullerene attempting to reintercalate. The strongest hysteresis is for intercalated blend films with excess fullerene loading ratio, which form a distinct nanoribbon morphology and exhibit a reduced geminate recombination rate. These results reveal that careful consideration should be taken during device fabrication, as postdeposition thermal treatments significantly impact the charge generation and recombination dynamics.
The construction of nano-sized, two-dimensionally ordered nanoparticle (NP) superstructures is important for various advanced applications such as photonics, sensing, catalysis, or nano-circuitry. Currently, such structures are fabricated using the templated organization approach, in which the templates are mainly created by photo-lithography or laser-lithography and other invasive top-down etching procedures. In this work, we present an alternative bottom-up preparation method for the controlled deposition of NPs into hierarchical structures. Lamellar polystyrene-block-poly(2-vinylpyridinium) thin films featuring alternating stripes of neutral PS and positively charged P2VP domains serve as templates, allowing for the selective adsorption of negatively charged gold NPs. Dense NP assembly is achieved by a simple immersion process, whereas two-dimensionally ordered arrays of NPs are realized by microcontact printing (mu CP), utilizing periodic polydimethylsiloxane wrinkle grooves loaded with gold NPs. This approach enables the facile construction of hierarchical NP arrays with variable geometries. Copyright (C) 2016 John Wiley & Sons, Ltd.
Background
Foot orthoses are usually assumed to be effective by optimizing mechanically dynamic rearfoot configuration. However, the effect from a foot orthosis on kinematics that has been demonstrated scientifically has only been marginal. The aim of this study was to examine the effect of different heights in medial arch-supported foot orthoses on rear foot motion during gait.
Methods
Nineteen asymptomatic runners (36±11years, 180±5cm, 79±10kg; 41±22km/week) participated in the study. Trials were recorded at 3.1 mph (5 km/h) on a treadmill. Athletes walked barefoot and with 4 different not customized medial arch-supported foot orthoses of various arch heights (N:0 mm, M:30 mm, H:35 mm, E:40mm). Six infrared cameras and the `Oxford Foot Model´ were used to capture motion. The average stride in each condition was calculated from 50 gait cycles per condition. Eversion excursion and internal tibia rotation were analyzed. Descriptive statistics included calculating the mean ± SD and 95% CIs. Group differences by condition were analyzed by one factor (foot orthoses) repeated measures ANOVA (α = 0.05).
Results
Eversion excursion revealed the lowest values for N and highest for H (B:4.6°±2.2°; 95% CI [3.1;6.2]/N:4.0°±1.7°; [2.9;5.2]/M:5.2°±2.6°; [3.6;6.8]/H:6.2°±3.3°; [4.0;8.5]/E:5.1°±3.5°; [2.8;7.5]) (p>0.05). Range of internal tibia rotation was lowest with orthosis H and highest with E (B:13.3°±3.2°; 95% CI [11.0;15.6]/N:14.5°±7.2°; [9.2;19.6]/M:13.8°±5.0°; [10.8;16.8]/H:12.3°±4.3°; [9.0;15.6]/E:14.9°±5.0°; [11.5;18.3]) (p>0.05). Differences between conditions were small and the intrasubject variation high.
Conclusion
Our results indicate that different arch support heights have no systematic effect on eversion excursion or the range of internal tibia rotation and therefore might not exert a crucial influence on rear foot alignment during gait.
A maximum entropy (MaxEnt) method is developed to predict flow rates or pressure gradients in hydraulic pipe networks without sufficient information to give a closed-form (deterministic) solution. This methodology substantially extends existing deterministic flow network analysis methods. It builds on the MaxEnt framework previously developed by the authors. This study uses a continuous relative entropy defined on a reduced parameter set, here based on the external flow rates. This formulation ensures consistency between different representations of the same network. The relative entropy is maximized subject to observable constraints on the mean values of a subset of flow rates or potential differences, the frictional properties of each pipe, and physical constraints arising from Kirchhoff’s first and second laws. The new method is demonstrated by application to a simple one-loop network and a 1,123-node, 1,140-pipe water distribution network in the suburb of Torrens, Australian Capital Territory, Australia.
Mutations in the gene encoding for filaggrin (FLG) are major predisposing factors for atopic dermatitis (AD). Besides genetic predisposition, immunological dysregulations considerably contribute to its pathophysiology. For example, thymic stromal lymphopoietin (TSLP) is highly expressed in lesional atopic skin and significantly contributes to the pathogenesis of AD by activating dendritic cells that then initiate downstream effects on, for example, T cells. However, little is known about the direct interplay between TSLP, filaggrin-deficient skin and other immune cells such as T lymphocytes. In the present study, FLG knockdown skin equivalents, characterised by intrinsically high TSLP levels, were exposed to activated CD4(+) T cells. T cell exposure resulted in an inflammatory phenotype of the skin equivalents. Furthermore, a distinct shift from a Th1/Th17 to a Th2/Th22 profile was observed following exposure of T cells to filaggrin-deficient skin equivalents. Interestingly, TSLP directly stimulated T cell migration exclusively in filaggrin-deficient skin equivalents even in the absence of dendritic cells, indicating a hitherto unknown role of TSLP in the pathogenesis of AD.
Information about the hydrological behaviour of a river basin prior to setting up, calibrating and validating a distributed hydrological model requires extensive datasets that are hardly available for many parts of the world due to insufficient monitoring networks. In this study, the focus was on prevailing spatio-temporal patterns of remotely sensed evapotranspiration (ET) that enabled conclusions to be drawn about the hydrological behaviour and spatial peculiarities of a river basin at rather high spatial resolution. The prevailing spatio-temporal patterns of ET were identified using a principal component analysis of a time series of 644 images of MODIS ET covering the Wami River basin (Tanzania) between the years 2000 and 2013. The time series of the loadings on the principal components were analysed for seasonality and significant long-term trends. The spatial patterns of principal component scores were tested for significant correlation with elevations and slopes, and for differences between different soil texture and land use classes. The results inferred that the temporal and spatial patterns of ET were related to those of preceding rainfalls. At the end of the dry season, high ET was maintained only in areas of shallow groundwater and in cloud forest nature reserves. A region of clear reduction of ET in the long-term was related to massive land use change. The results also confirmed that most soil texture and land use classes differed significantly. Moreover, ET was exceptionally high in natural forests and loam soil, and very low in bushland and sandy-loam soil. Clearly, this approach has shown great potential of publicly available remote sensing data in providing a sound basis for water resources management as well as for distributed hydrological models in data-scarce river basins at lower latitudes.
The low surface-charge stability of polypropylene (PP) frequently limits its application as an electret material. In this paper, we demonstrate how the treatment of PP-film surfaces with orthophosphoric acid (H3PO4) enhances their charge stability. To discriminate between the effects of chemical modification and thermal treatment, as-received and annealed PP films are used as reference samples. The electret properties of treated and non-treated PP films are characterized with thermally stimulated discharge (TSD) and isothermal surface-potential decay (ISPD) experiments, from which considerable improvement in thermal and temporal charge stability is observed for samples modified with H3PO4. The half-value temperature (T-1/2) observed on TSD curves of chemically treated PP increases to 131 and 145 degrees C for positive and negative charges, respectively. The enhancement might be attributed to the phosphoric compounds detected on the H3PO4-modified surfaces via attenuated-total-reflection infrared spectroscopy. Deeper surface traps formed at the "foreign" phosphorus-containing structures are able to capture the charges over longer time periods and at higher temperatures, thus leading to significant improvements in the temporal and thermal surface-charge stabilities of PP electrets. Published by AIP Publishing.
Polydepsipeptide Block-Stabilized Polyplexes for Efficient Transfection of Primary Human Cells
(2017)
The rational design of a polyplex gene carrier aims to balance maximal effectiveness of nucleic acid transfection into cells with minimal adverse effects. Depsipeptide blocks with an M (n) similar to 5 kDa exhibiting strong physical interactions were conjugated with PEI moieties (2.5 or 10 kDa) to di- and triblock copolymers. Upon nanoparticle formation and complexation with DNA, the resulting polyplexes (sizes typically 60-150 nm) showed remarkable stability compared to PEI-only or lipoplex and facilitated efficient gene delivery. Intracellular trafficking was visualized by observing fluorescence-labeled pDNA and highlighted the effective cytoplasmic uptake of polyplexes and release of DNA to the perinuclear space. Specifically, a triblock copolymer with a middle depsipeptide block and two 10 kDa PEI swallowtail structures mediated the highest levels of transgenic VEGF secretion in mesenchymal stem cells with low cytotoxicity. These nanocarriers form the basis for a delivery platform technology, especially for gene transfer to primary human cells.
The concept of a Global Monsoon (GM) has been proposed based on modern precipitation observations, but its application over a wide range of temporal scales is still under debate. Here, we present a synthesis of 268 continental paleo-moisture records collected from monsoonal systems in the Eastern Hemisphere, including the East Asian Monsoon (EAsM), the Indian Monsoon (IM), the East African Monsoon (EAfM), and the Australian Monsoon (AuM) covering the last 18,000 years. The overall pattern of late Glacial to Holocene moisture change is consistent with those inferred from ice cores and marine records. With respect to the last 10,000 years (10 ka), i.e. a period that has high spatial coverage, a Fuzzy c-Means clustering analysis of the moisture index records together with "Xie-Beni" index reveals four clusters of our data set. The paleoclimatic meaning of each cluster is interpreted considering the temporal evolution and spatial distribution patterns. The major trend in the tropical AuM, EAfM, and IM regions is a gradual decrease in moisture conditions since the early Holocene. Moisture changes in the EAsM regions show maximum index values between 8 and 6 ka. However, records located in nearby subtropical areas, i.e. in regions not influenced by the intertropical convergence zone, show an opposite trend compared to the tropical monsoon regions (AuM, EAfM and IM), i.e. a gradual increase. Analyses of modern meteorological data reveal the same spatial patterns as in the paleoclimate records such that, in times of overall monsoon strengthening, lower precipitation rates are observed in the nearby subtropical areas. We explain this pattern as the effect of a strong monsoon circulation suppressing air uplift in nearby subtropical areas, and hence hindering precipitation. By analogy to the modern system, this would mean that during the early Holocene strong monsoon period, the intensified ascending airflows within the monsoon domains led to relatively weaker ascending or even descending airflows in the adjacent subtropical regions, resulting in a precipitation deficit compared to the late Holocene. Our conceptual model therefore integrates regionally contrasting moisture changes into the Global Monsoon hypothesis. (C) 2017 Elsevier Ltd. All rights reserved.
The paper presents the Polish study Ty-wy-pan. Kartka z dziejów
próżności ludzkiej (‘You (singular)–you (plural)–Lord. An overview on the history of the people’s vanity’, 1916) by Alexander Brückner from a linguistic-pragmatical as well as ideological point of view. In his pioneer study on politeness, the German-Polish slavist Brückner (1856–1939) critically reflects on the current system of Polish addresses and titles, especially in relating to the soon-to-be
refoundation of the Second Polish Republic (1918). The paper analyzes how his linguistic description and his ideas for reformation of the Polish addressative system are pragmatically justified and how they are ideologically motivated.
Furthermore, the paper reconstructs the status of Brückner’s concept of politeness in the context of current studies on Polish pragmatics.
Academic personal initiative (API) has rarely been studied with regard to literacy development. The purpose of this longitudinal study was therefore to examine the unique effects of API on the development of word comprehension as an indicator of word reading. To this end, the effects of previous word comprehension, intrinsic reading motivation, and basic cognitive ability (i.e., processing speed) were controlled for. A total of 1,515 German students participated in a longitudinal assessment starting in Grades 1 to 3, with a second point of measurement nine months later. Latent change score analyses revealed positive associations between API and gains in word comprehension, both in the total sample and at all grade levels. These relations were robust against the effects of previous word comprehension and intrinsic reading motivation. The findings suggest that children play an active role in their own reading development. (C) 2017 Elsevier Inc. All rights reserved.
Personal initiative
(2017)
Although the effects of personal initiative (PI) on adults' performance and other favorable outcomes are well documented, research has only recently begun to study PI in childhood. This study aimed at examining the development of PI, its predictors, and its developmental effects from childhood to early adolescence. A total of 1,593 German children participated in a longitudinal study starting at Grades 2 to 4, with a second measurement wave two years later. Latent change score analyses revealed that 1) children differed significantly in their change scores of PI, that 2) executive functions and positive parenting predicted change scores in PI, and that 3) high initial levels and change scores in PI reduced the development of internalizing and externalizing problems and supported the development of prosocial behavior and academic competencies. These findings endorse the plasticity of PI and shed light on the active part of children in promoting their own development.
The standard model for GRB afterglow emission treats the accelerated electron population as a simple power law, N(E) proportional to E-p for p greater than or similar to 2. However, in standard Fermi shock acceleration, a substantial fraction of the swept-up particles do not enter the acceleration process at all. Additionally, if acceleration is efficient, then the nonlinear back-reaction of accelerated particles on the shock structure modifies the shape of the nonthermal tail of the particle spectra. Both of these modifications to the standard synchrotron afterglow impact the luminosity, spectra, and temporal variation of the afterglow. To examine the effects of including thermal particles and nonlinear particle acceleration on afterglow emission, we follow a hydrodynamical model for an afterglow jet and simulate acceleration at numerous points during the evolution. When thermal particles are included, we find that the electron population is at no time well fitted by a single power law, though the highest-energy electrons are; if the acceleration is efficient, then the power-law region is even smaller. Our model predicts hard-soft-hard spectral evolution at X-ray energies, as well as an uncoupled X-ray and optical light curve. Additionally, we show that including emission from thermal particles has drastic effects (increases by factors of 100 and 30, respectively) on the observed flux at optical and GeV energies. This enhancement of GeV emission makes afterglow detections by future gamma-ray observatories, such as CTA, very likely.
Hauptziel Adipositas ist eine der Hauptindikationen in der Kinder- und Jugend-Rehabilitation. Für ältere Jugendliche und junge Erwachsene fehlen altersspezifische Therapieangebote fast vollständig. Ziel war es die Wünsche bezüglich der Inhalte und Methoden einer „perfekten Therapie“ im Rahmen eines Rehabilitationsaufenthalts zu untersuchen.
Methode Im Rahmen der YOUTH-Studie wurden 147 adipöse Jugendliche und junge Erwachsene beiderlei Geschlechts (zwischen 15 und 21 Jahren) mithilfe eines standardisierten Fragebogens befragt.
Ergebnis Insgesamt zeigten sich relativ wenige alters- und geschlechtsspezifische Unterschiede. Interdisziplinär geleitete, koedukative Gruppen mit Elterneinbindung wurden gewünscht. Wichtige Themen waren gesunde Ernährung sowie psychosoziale Aspekte. Auch der Prävention von Rückfällen wurde eine hohe Relevanz zugeschrieben.
Schlussfolgerung Psychosoziale Aspekte und die Vorbereitung auf mögliche Rückfallsituationen sollten integraler Bestandteil der Therapie sein.
Battle of plates
(2017)
Objective: Approach-avoidance training (AAT) is a promising approach in obesity treatment. The present study examines whether an AAT is feasible and able to influence approach tendencies in children and adolescents, comparing implicit and explicit training approaches. Design/Setting/Subjects: Fifty-nine overweight children and adolescents (aged 8-16 years; twenty-six boys) participated in an AAT for food cues, learning to reject snack items and approach vegetable items. Reaction times in the AAT and an implicit association rest (IAT) were assessed pre- and post-intervention. Results: A significant increase in the AAT compatibility scores with a large effect (eta(2) = 0.18) was found. No differences between the implicit and explicit training approaches and no change in the IAT scores were observed. Conclusions: Automatic tendencies in children can be trained, too. The implementation of AAT in the treatment of obesity might support the modification of an unhealthy nutrition behaviour pattern. Further data from randomized controlled clinical trials are needed.
Clinical supervision is regarded as one of the most important components of psychotherapy training. In clinical practice, it has been found that the implementation of clinical supervision varies substantially and often differs from the recommendations made in the literature. The objective of the current study was to investigate the frequency of topics (e.g. ethical issues) and techniques (e.g. role play) in the clinical supervision of psychotherapy trainees in Germany. To this end, we considered supervisions in cognitive behavioural therapy (CBT) and psychodynamic therapy (PT). A total of 791 psychotherapy trainees (533 CBT and 242 PT) were asked via the internet to provide information about their current supervision sessions. We found that clinical supervision in psychotherapy training addressed topics that are central for the effective treatment of supervised patients (i.e. therapeutic interventions, therapeutic alliance, maintaining factors, and therapeutic goals). However, the most frequently used intervention in clinical supervision in psychotherapy training was case discussion. Rarely were techniques used that allowed the supervisor to give the supervisee feedback based on the supervisee's demonstrated competencies. For example, 46% of the supervisors never used audiotapes or videotapes in the supervision. Differences between CBT and PT were rather small. Current practice regarding the techniques used in clinical supervision for psychotherapy trainees contradicts recommendations for active and feedback-oriented clinical supervision. Thus the potential of clinical supervision might not be fully used in clinical practice.
Objective: Cognitive-behavioral therapy (CBT) has been shown to be effective in treating hypochondriasis. However, there are doubts regarding the long-term effectiveness of CBT for hypochondriasis, in particular for follow-up periods longer than 1 year. The aim of the present study was to evaluate the long-term effectiveness of cognitive therapy (CT) and exposure therapy (ET) for the treatment of hypochondriasis. Method: Seventy-five patients with a diagnosis of hypochondriasis who were previously treated with CT or ET were contacted 3 years after treatment. Fifty (67%) patients participated and were interviewed by an independent and blinded diagnostician using standardized interviews. Results: We found further improvements after therapy in primary outcome measures (d = .37), general functioning (d = .38), and reduced doctor visits (d = .30) during the naturalistic follow-up period. At the 3-year follow-up, 72% of the patients no longer fulfilled the diagnosis of hypochondriasis. Based on the main outcome measure, we found response rates of 76% and remission rates of 68%. At follow-up, only 4% of patients were taking antidepressant medication. Additional psychological treatment was utilized by 18% of the patients during the follow-up period (only 8% because of health anxiety). We found no overall differences between CT and ET. Only a trend for a greater deterioration rate in CT (13%) in comparison to ET (0%) was found. Conclusions: Our results suggest that 2/3 of the patients with hypochondriasis were remitted in the long term. Thus, remission rates after CBT were twice as high as in untreated samples.
Previous studies found high prevalence rates of personality disorders (PDs) in patients with hypochondriasis; however, assessment was often based only on questionnaires. In the current study, a sample of 68 patients with hypochondriasis was compared to 31 patients with panic disorder and to 94 healthy controls. Participants were investigated with the Structured Clinical Interview for DSM-IV Personality Disorders questionnaire (SCID-II questionnaire) and the SCID-II interview. Based on the cut-off scores of the SCID-II questionnaire, we found a prevalence rate of 45.6% for PD in patients with hypochondriasis. In comparison to healthy controls, patients with hypochondriasis showed characteristics of paranoid, borderline, avoid ant, and-dependent PDs in the dimensional assessment significantly more often. However, no significant differences were found between the clinical samples. Based on the SCID-II interview, only 2.9% of the patients with hypochondriasis fulfilled the criteria for a PD. These results suggest that PDs are not a specific characteristic of hypochondriasis.
The illness-related evaluation of bodily symptoms is considered to be an important maintaining factor in somatoform disorders. However, little is known about context variables that could influence this evaluation process. In the current study, participants completed three versions of the Health Norms Sorting Task (HNST) and evaluated bodily symptoms in different contexts (i.e., different evaluation perspectives and time frames of evaluation). Additionally, the three HNST versions were presented in different orders. Bodily symptoms were evaluated more often as a sign of illness when a specific time frame (i.e., one week) was given. However, this context effect was only large when participants had previously evaluated symptoms existing without a concrete duration. Thus, previously completed symptom evaluations appear to represent an important frame of reference in terms of a cue that makes specific context variables salient. The results further suggested that these cueing effects might be less relevant for participants with elevated somatic symptom reports.
This review analyzes the potential role and long-term effects of field perennial polycultures (mixtures) in agricultural systems, with the aim of reducing the trade-offs between provisioning and regulating ecosystem services. First, crop rotations are identified as a suitable tool for the assessment of the long-term effects of perennial polycultures on ecosystem services, which are not visible at the single-crop level. Second, the ability of perennial polycultures to support ecosystem services when used in crop rotations is quantified through eight agricultural ecosystem services. Legume-grass mixtures and wildflower mixtures are used as examples of perennial polycultures, and compared with silage maize as a typical crop for biomass production. Perennial polycultures enhance soil fertility, soil protection, climate regulation, pollination, pest and weed control, and landscape aesthetics compared with maize. They also score lower for biomass production compared with maize, which confirms the trade-off between provisioning and regulating ecosystem services. However, the additional positive factors provided by perennial polycultures, such as reduced costs for mineral fertilizer, pesticides, and soil tillage, and a significant preceding crop effect that increases the yields of subsequent crops, should be taken into account. However, a full assessment of agricultural ecosystem services requires a more holistic analysis that is beyond the capabilities of current frameworks.
Trait-based approaches have become increasingly successful in community ecology. They assume that the distribution of functional traits within communities responds in a predictable way to alterations in environmental forcing and that strong forcing may accelerate such trait changes. We used high frequency measurements of phytoplankton to test these assumptions. We analyzed the seasonal and long-term dynamics of the community trait mean within a multi-dimensional trait space under alternating multifactorial environmental conditions. The community trait mean exhibited a distinct recurrent annual pattern that reflected minor changes in climate, herbivory and nutrients. Independent of early spring conditions, the community trait mean was repeatedly driven into a narrow confined area in the trait space under pronounced herbivory during the clear water phase. The speed of movement was highest at the onset and the relaxation of such strong unidirectional forcing. Thus, our data support the conceptual framework of trait-based ecology that alterations in environmental conditions are systematically tracked by adjustments in the dominant functional trait values and that the speed of trait changes depends on the kind and intensity of the selection pressure. Our approach provides a sensitive tool to detect small functional differences in the community related to subtle differences in forcing.
The invasion success of the cyanobacterium Cylindrospermopsis raciborskii in experimental mesocosms
(2017)
The potentially toxic, invasive cyanobacterium Cylindrospermopsis raciborskii, originating from sub-tropical regions, has spread into temperate climate zones in almost all continents. Potential factors in its success are temperature, light and nutrient levels. Grazing losses through zooplankton have been measured in the laboratory but are typically not regarded as a factor in (failed) invasion success. In some potentially suitable lakes, C. raciborskii has never been found, although it is present in water bodies close by. Therefore, we tested the invasive potential of three different isolates introduced into natural plankton communities using laboratory mesocosm experiments under three grazing levels: ambient zooplankton densities, removal of large species using 100 mu m mesh and a ca. doubling of large species. Three C. raciborskii isolates originating from the same geographic region (North-East Germany) were added separately to the four replicates of each treatment and kept in semi-continuous cultures for 21 days. Two isolates disappeared from the mesocosms and were also not viable in filtered lake water indicating that the lake water itself or the switch from culture medium to lake water led to the decay of the inoculated C. raciborskii. Only one out of the three isolates persisted in the plankton communities at a rather low level and only in the treatment without larger zooplankton. This result demonstrates that under potentially suitable environmental conditions, top-down control from zooplankton might hamper the establishment of C. raciborskii. Non-metric multidimensional scaling showed distinct variation in resident phytoplankton communities between the different grazing levels, thus differential grazing impact shaped the resident community in different ways allowing C. raciborskii only to invade under competitive (= low grazing pressure) conditions. Furthermore, even after invasion failure, the temporary presence of C. raciborskii influenced the phytoplankton community.