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„Die Beiträge in diesem Band beleuchten aus verschiedenen Perspektiven die (…) Veränderungen der Sprachwissenschaft im Zuge des linguistic turn. Sie gehen zurück auf ein Festkolloquium zu Ehren des 65. Geburtstages von Joachim Gessinger, das am 25. und 26. Juni 2010 in Potsdam stattgefunden hat. Ziel des Kolloquiums war es, Ansätze, Theoriebildungen und methodische Zugriffe in der Sprachwissenschaft seit dem linguistic turn in den Blick zu nehmen. Diese Frage nach einer Standortbestimmung der sprachwissenschaftlichen Forschung in Deutschland steht auch im Mittelpunkt der nun publizierten Fassung der Beiträge, die von Vertreterinnen und Vertretern ausgewählter Teildisziplinen stammen, die die inhaltliche, theoretische und methodische Ausrichtung ihres Forschungsfeldes reflektieren.“ (Manuela Böhm, Elisabeth Berner & Jürgen Erfurt, OBST 78: S. 13)
Inhalt:
Manuela Böhm, Elisabeth Berner & Jürgen Erfurt: Nach dem Turn ist vor dem Turn. Ein Prolog;
Michael Elmentaler: Zur Pragmatisierung der Sprachgeschichte. Eine Standortbestimmung anhand neuerer Sprachgeschichten des Deutschen;
Ingrid Schröder: Dialekte im Kontakt. Individuelle Ausformungen des Sprachrepertoires;
Bernd Pompino-Marschall: Die rezente Entwicklung in der Phonetik: Vom verbrannten Zeigefinger zu Praat;
Gisbert Fanselow: Kann die Linguistik das Jahr 2024 erleben? Und die Syntax das Jahr 2014?;
Elke Nowak: Nach dem linguistic turn – die neue Wissenschaft von der Sprache und die Sprachen;
Utz Maas: Linguistische Schattenspiele: sprachwissenschaftliche Arbeiten zur Schriftkultur;
Ulrich Schmitz: Linguistica ancilla mediorum? Sprachwissenschaft und Medien 1960-2010: Von kühler Distanz zu teilnehmender Beobachtung & von Textmaterial zu multimodaler Verblendung;
Eduard Haueis: Didaktik und Linguistik: Wie die Modellierung sprachlichen Wissens und Könnens mit dem Bestehenbleiben oder dem Überwinden von Bildungsschranken zusammenhängt;
Joachim Gessinger: Vor dem linguistic turn. Ein Epilog
Kreise - Punkte - Linien
(2015)
The current study investigates to what extent masked morphological priming is modulated by language-particular properties, specifically by its writing system. We present results from two masked priming experiments investigating the processing of complex Japanese words written in less common (moraic) scripts. In Experiment 1, participants performed lexical decisions on target verbs; these were preceded by primes which were either (i) a past-tense form of the same verb, (ii) a stem-related form with the epenthetic vowel -i, (iii) a semantically-related form, and (iv) a phonologically-related form. Significant priming effects were obtained for prime types (i), (ii), and (iii), but not for (iv). This pattern of results differs from previous findings on languages with alphabetic scripts, which found reliable masked priming effects for morphologically related prime/target pairs of type (i), but not for non-affixal and semantically-related primes of types (ii), and (iii). In Experiment 2, we measured priming effects for prime/target pairs which are neither morphologically, semantically, phonologically nor - as presented in their moraic scripts—orthographically related, but which—in their commonly written form—share the same kanji, which are logograms adopted from Chinese. The results showed a significant priming effect, with faster lexical-decision times for kanji-related prime/target pairs relative to unrelated ones. We conclude that affix-stripping is insufficient to account for masked morphological priming effects across languages, but that language-particular properties (in the case of Japanese, the writing system) affect the processing of (morphologically) complex words.
Species can adjust their traits in response to selection which may strongly influence species coexistence. Nevertheless, current theory mainly assumes distinct and time-invariant trait values. We examined the combined effects of the range and the speed of trait adaptation on species coexistence using an innovative multispecies predator–prey model. It allows for temporal trait changes of all predator and prey species and thus simultaneous coadaptation within and among trophic levels. We show that very small or slow trait adaptation did not facilitate coexistence because the stabilizing niche differences were not sufficient to offset the fitness differences. In contrast, sufficiently large and fast trait adaptation jointly promoted stable or neutrally stable species coexistence. Continuous trait adjustments in response to selection enabled a temporally variable convergence and divergence of species traits; that is, species became temporally more similar (neutral theory) or dissimilar (niche theory) depending on the selection pressure, resulting over time in a balance between niche differences stabilizing coexistence and fitness differences promoting competitive exclusion. Furthermore, coadaptation allowed prey and predator species to cluster into different functional groups. This equalized the fitness of similar species while maintaining sufficient niche differences among functionally different species delaying or preventing competitive exclusion. In contrast to pre-
vious studies, the emergent feedback between biomass and trait dynamics enabled supersaturated coexistence for a broad range of potential trait adaptation and parameters. We conclude that accounting for trait adaptation may explain stable and supersaturated species coexistence for a broad range of environmental conditions in natural systems when the absence of such adaptive changes would preclude it. Small trait changes, coincident with those that may occur within many natural populations, greatly enlarged the number of coexisting species.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
Der Beitrag rekonstruiert erstens den humanistischen Begriff der Dichtung bei Melanchthon. Dichtung erscheint hier als Medium zur Vermittlung insbesondere moralpädagogischer Inhalte, das sich vor allem durch seine Versform von anderen sprachlichen Vermittlungsformen unterscheidet. Dieser Dichtungsbegriff wird zweitens mit dem neuplatonischen Begriff der Dichtung als Ergebnis einer göttlichen Inspiration (Enthusiasmus) konfrontiert, wie ihn Marsilio Ficino entwickelt hat. In Deutschland haben insbesondere Konrad Celtis und seine Schüler diesen Dichtungsbegriff vertreten, besonders prominent etwas Matthäus Lupinus Calidomius und Jacob Locher. In einem dritten Schritt zeigt der Beitrag, dass dieser Dichtungsbegriff aus theologischen Gründen im Protestantismus nicht mehr zu vertreten war: das reformatorische Postulat des sola scriptura verbot jede Berufung auf eine göttliche Inspiration außerhalb der Bibel.
Two experiments examined how individuals respond to a restriction presented within an approach versus an avoidance frame. In Study 1, working on a problem-solving task, participants were initially free to choose their strategy, but for a second task were told to change their strategy. The message to change was embedded in either an approach or avoidance frame. When confronted with an avoidance compared to an approach frame, the participants’ reactance toward the request was greater and, in turn, led to impaired performance. The role of reactance as a response to threat to freedom was explicitly examined in Study 2, in which participants evaluated a potential change in policy affecting their program of study herein explicitly varying whether a restriction was present or absent and whether the message was embedded in an approach versus avoidance frame. When communicated with an avoidance frame and as a restriction, participants showed the highest resistance in terms of reactance, message agreement and evaluation of the communicator. The difference in agreement with the change was mediated by reactance only when a restriction was present. Overall, avoidance goal frames were associated with more resistance to change on different levels of experience (reactance, performance, and person perception). Reactance mediated the effect of goal frame on other outcomes only when a restriction was present.
Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several “onium” cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and gK) of the tensors could be determined and information on the structural changes in the [CuBr4]2- anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.
Compared to their inorganic counterparts, organic semiconductors suffer from relatively low charge carrier mobilities. Therefore, expressions derived for inorganic solar cells to correlate characteristic performance parameters to material properties are prone to fail when applied to organic devices. This is especially true for the classical Shockley-equation commonly used to describe current-voltage (JV)-curves, as it assumes a high electrical conductivity of the charge transporting material. Here, an analytical expression for the JV-curves of organic solar cells is derived based on a previously published analytical model. This expression, bearing a similar functional dependence as the Shockley-equation, delivers a new figure of merit α to express the balance between free charge recombination and extraction in low mobility photoactive materials. This figure of merit is shown to determine critical device parameters such as the apparent series resistance and the fill factor.
Background
The efficiency of multiplex editing in plants by the RNA-guided Cas9 system is limited by efficient introduction of its components into the genome and by their activity. The possibility of introducing large fragment deletions by RNA-guided Cas9 tool provides the potential to study the function of any DNA region of interest in its ‘endogenous’ environment.
Results
Here, an RNA-guided Cas9 system was optimized to enable efficient multiplex editing in Arabidopsis thaliana. We demonstrate the flexibility of our system for knockout of multiple genes, and to generate heritable large-fragment deletions in the genome. As a proof of concept, the function of part of the second intron of the flower development gene AGAMOUS in Arabidopsis was studied by generating a Cas9-free mutant plant line in which part of this intron was removed from the genome. Further analysis revealed that deletion of this intron fragment results 40 % decrease of AGAMOUS gene expression without changing the splicing of the gene which indicates that this regulatory region functions as an activator of AGAMOUS gene expression.
Conclusions
Our modified RNA-guided Cas9 system offers a versatile tool for the functional dissection of coding and non-coding DNA sequences in plants.
Walking while concurrently performing cognitive and/or motor interference tasks is the norm rather than the exception during everyday life and there is evidence from behavioral studies that it negatively affects human locomotion. However, there is hardly any information available regarding the underlying neural correlates of single- and dual-task walking. We had 12 young adults (23.8 ± 2.8 years) walk while concurrently performing a cognitive interference (CI) or a motor interference (MI) task. Simultaneously, neural activation in frontal, central, and parietal brain areas was registered using a mobile EEG system. Results showed that the MI task but not the CI task affected walking performance in terms of significantly decreased gait velocity and stride length and significantly increased stride time and tempo-spatial variability. Average activity in alpha and beta frequencies was significantly modulated during both CI and MI walking conditions in frontal and central brain regions, indicating an increased cognitive load during dual-task walking. Our results suggest that impaired motor performance during dual-task walking is mirrored in neural activation patterns of the brain. This finding is in line with established cognitive theories arguing that dual-task situations overstrain cognitive capabilities resulting in motor performance decrements.
Dependency Resolution Difficulty Increases with Distance in Persian Separable Complex Predicates
(2016)
Delaying the appearance of a verb in a noun-verb dependency tends to increase processing difficulty at the verb; one explanation for this locality effect is decay and/or interference of the noun in working memory. Surprisal, an expectation-based account, predicts that delaying the appearance of a verb either renders it no more predictable or more predictable, leading respectively to a prediction of no effect of distance or a facilitation. Recently, Husain et al. (2014) suggested that when the exact identity of the upcoming verb is predictable (strong predictability), increasing argument-verb distance leads to facilitation effects, which is consistent with surprisal; but when the exact identity of the upcoming verb is not predictable (weak predictability), locality effects are seen. We investigated Husain et al.'s proposal using Persian complex predicates (CPs), which consist of a non-verbal element—a noun in the current study—and a verb. In CPs, once the noun has been read, the exact identity of the verb is highly predictable (strong predictability); this was confirmed using a sentence completion study. In two self-paced reading (SPR) and two eye-tracking (ET) experiments, we delayed the appearance of the verb by interposing a relative clause (Experiments 1 and 3) or a long PP (Experiments 2 and 4). We also included a simple Noun-Verb predicate configuration with the same distance manipulation; here, the exact identity of the verb was not predictable (weak predictability). Thus, the design crossed Predictability Strength and Distance. We found that, consistent with surprisal, the verb in the strong predictability conditions was read faster than in the weak predictability conditions. Furthermore, greater verb-argument distance led to slower reading times; strong predictability did not neutralize or attenuate the locality effects. As regards the effect of distance on dependency resolution difficulty, these four experiments present evidence in favor of working memory accounts of argument-verb dependency resolution, and against the surprisal-based expectation account of Levy (2008). However, another expectation-based measure, entropy, which was computed using the offline sentence completion data, predicts reading times in Experiment 1 but not in the other experiments. Because participants tend to produce more ungrammatical continuations in the long-distance condition in Experiment 1, we suggest that forgetting due to memory overload leads to greater entropy at the verb.
Different systems for habitual versus goal-directed control are thought to underlie human decision-making. Working memory is known to shape these decision-making systems and
their interplay, and is known to support goal-directed decision making even under stress. Here, we investigated if and how decision systems are differentially influenced by breaks filled with diverse everyday life activities known to modulate working memory performance. We used a within-subject design where young adults listened to music and played a video game during breaks interleaved with trials of a sequential two-step Markov decision task, designed to assess habitual as well as goal-directed decision making. Based on a neurocomputational model of task performance, we observed that for individuals with a rather limited
working memory capacity video gaming as compared to music reduced reliance on the goal-directed decision-making system, while a rather large working memory capacity prevented such a decline. Our findings suggest differential effects of everyday activities on key decision-making processes.
We tested the influence of two light intensities [40 and 300 μmol PAR / (m2s)] on the fatty acid composition of three distinct lipid classes in four freshwater phytoplankton species. We chose species of different taxonomic classes in order to detect potentially similar reaction characteristics that might also be present in natural phytoplankton communities. From samples of the bacillariophyte Asterionella formosa, the chrysophyte Chromulina sp., the cryptophyte Cryptomonas ovata and the zygnematophyte Cosmarium botrytis we first separated glycolipids (monogalactosyldiacylglycerol, digalactosyldiacylglycerol, and sulfoquinovosyldiacylglycerol), phospholipids (phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, phosphatidylinositol, and phosphatidylserine) as well as non-polar lipids (triacylglycerols), before analyzing the fatty acid composition of each lipid class. High variation in the fatty acid composition existed among different species. Individual fatty acid compositions differed in their reaction to changing light intensities in the four species. Although no generalizations could be made for species across taxonomic classes, individual species showed clear but small responses in their ecologically-relevant omega-3 and omega-6 polyunsaturated fatty acids (PUFA) in terms of proportions and of per tissue carbon quotas. Knowledge on how lipids like fatty acids change with environmental or culture conditions is of great interest in ecological food web studies, aquaculture, and biotechnology, since algal lipids are the most important sources of omega-3 long-chain PUFA for aquatic and terrestrial consumers, including humans.
We examined the effects of argument-head distance in SVO and SOV languages (Spanish and German), while taking into account readers' working memory capacity and controlling for expectation (Levy, 2008) and other factors. We predicted only locality effects, that is, a slowdown produced by increased dependency distance (Gibson, 2000; Lewis and Vasishth, 2005). Furthermore, we expected stronger locality effects for readers with low working memory capacity. Contrary to our predictions, low-capacity readers showed faster reading with increased distance, while high-capacity readers showed locality effects. We suggest that while the locality effects are compatible with memory-based explanations, the speedup of low-capacity readers can be explained by an increased probability of retrieval failure. We present a computational model based on ACT-R built under the previous assumptions, which is able to give a qualitative account for the present data and can be tested in future research. Our results suggest that in some cases, interpreting longer RTs as indexing increased processing difficulty and shorter RTs as facilitation may be too simplistic: The same increase in processing difficulty may lead to slowdowns in high-capacity readers and speedups in low-capacity ones. Ignoring individual level capacity differences when investigating locality effects may lead to misleading conclusions.
Die These des Aufsatzes lautet, dass es sich bei Sebastian Brants „Narrenschiff“ um einen Text handelt, der entsprechend der Prinzipien verstanden werden kann, die Rudolf Agricola für das Sammeln von Argumenten formuliert hat. Das Gründungsdokument dieser humanistischen Methode, die unter dem Begriff der „loci communes“ Geschich¬te gemacht hat, ist ein Brief Agricolas aus dem Jahr 1484. Ein erster Teil des Aufsatzes stellt Agricolas Argumen¬tationstheorie dar, ein zweiter Teil zeigt, dass Brants „Narrenschiff“ als Ergebnis dieser Argumentationstheorie verstanden werden kann.
'Gelegenheitsdichtung'
(2010)
The gravitational field of a laser pulse of finite lifetime, is investigated in the framework of linearized gravity. Although the effects are very small, they may be of fundamental physical interest. It is shown that the gravitational field of a linearly polarized light pulse is modulated as the norm of the corresponding electric field strength, while no modulations arise for circular polarization. In general, the gravitational field is independent of the polarization direction. It is shown that all physical effects are confined to spherical shells expanding with the speed of light, and that these shells are imprints of the spacetime events representing emission and absorption of the pulse. Nearby test particles at rest are attracted towards the pulse trajectory by the gravitational field due to the emission of the pulse, and they are repelled from the pulse trajectory by the gravitational field due to its absorption. Examples are given for the size of the attractive effect. It is recovered that massless test particles do not experience any physical effect if they are co-propagating with the pulse, and that the acceleration of massless test particles counter-propagating with respect to the pulse is four times stronger than for massive particles
at rest. The similarities between the gravitational effect of a laser pulse and Newtonian gravity in two dimensions are pointed out. The spacetime curvature close to the pulse is compared to that induced by gravitational waves from astronomical sources.
Children’s interpretations of sentences containing focus particles do not seem adult-like until school age. This study investigates how German 4-year-old children comprehend sentences with the focus particle ‘nur’ (only) by using different tasks and controlling for the impact of general cognitive abilities on performance measures. Two sentence types with ‘only’ in either pre-subject or pre-object position were presented. Eye gaze data and verbal responses were collected via the visual world paradigm combined with a sentence-picture verification task. While the eye tracking data revealed an adult-like pattern of focus particle processing, the sentence-picture verification replicated previous findings of poor comprehension, especially for ‘only’ in pre-subject position. A second study focused on the impact of general cognitive abilities on the outcomes of the verification task. Working memory was related to children’s performance in both sentence types whereas inhibitory control was selectively related to the number of errors for sentences with ‘only’ in pre-subject position. These results suggest that children at the age of 4 years have the linguistic competence to correctly interpret sentences with focus particles, which–depending on specific task demands–may be masked by immature general cognitive abilities.
Recent research has indicated that university students sometimes use caffeine pills for neuroenhancement (NE; non-medical use of psychoactive substances or technology to produce a subjective enhancement in psychological functioning and experience), especially during exam preparation. In our factorial survey experiment, we manipulated the evidence participants were given about the prevalence of NE amongst peers and measured the resulting effects on the psychological predictors included in the Prototype-Willingness Model of risk behavior. Two hundred and thirty-one university students were randomized to a high prevalence condition (read faked research results overstating usage of caffeine pills amongst peers by a factor of 5; 50%), low prevalence condition (half the estimated prevalence; 5%) or control condition (no information about peer prevalence). Structural equation modeling confirmed that our participants’ willingness and intention to use caffeine pills in the next exam period could be explained by their past use of neuroenhancers, attitude to NE and subjective norm about use of caffeine pills whilst image of the typical user was a much less important factor. Provision of inaccurate information about prevalence reduced the predictive power of attitude with respect to willingness by 40-45%. This may be because receiving information about peer prevalence which does not fit with their perception of the social norm causes people to question their attitude. Prevalence information might exert a deterrent effect on NE via the attitude-willingness association. We argue that research into NE and deterrence of associated risk behaviors should be informed by psychological theory.
Filling the Silence
(2016)
In a self-paced reading experiment, we investigated the processing of sluicing constructions (“sluices”) whose antecedent contained a known garden-path structure in German. Results showed decreased processing times for sluices with garden-path antecedents as well as a disadvantage for antecedents with non-canonical word order downstream from the ellipsis site. A post-hoc analysis showed the garden-path advantage also to be present in the region right before the ellipsis site. While no existing account of ellipsis processing explicitly predicted the results, we argue that they are best captured by combining a local antecedent mismatch effect with memory trace reactivation through reanalysis.
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Background
Overweight and obesity are increasing health problems that are not restricted to adults only. Childhood obesity is associated with metabolic, psychological and musculoskeletal comorbidities. However, knowledge about the effect of obesity on the foot function across maturation is lacking. Decreased foot function with disproportional loading characteristics is expected for obese children. The aim of this study was to examine foot loading characteristics during gait of normal-weight, overweight and obese children aged 1-12 years.
Methods
A total of 10382 children aged one to twelve years were enrolled in the study. Finally, 7575 children (m/f: n = 3630/3945; 7.0 +/- 2.9yr; 1.23 +/- 0.19m; 26.6 +/- 10.6kg; BMI: 17.1 +/- 2.4kg/m(2)) were included for (complete case) data analysis. Children were categorized to normalweight (>= 3rd and <90th percentile; n = 6458), overweight (>= 90rd and <97th percentile; n = 746) or obese (>97th percentile; n = 371) according to the German reference system that is based on age and gender-specific body mass indices (BMI). Plantar pressure measurements were assessed during gait on an instrumented walkway. Contact area, arch index (AI), peak pressure (PP) and force time integral (FTI) were calculated for the total, fore-, mid-and hindfoot. Data was analyzed descriptively (mean +/- SD) followed by ANOVA/Welch-test (according to homogeneity of variances: yes/no) for group differences according to BMI categorization (normal-weight, overweight, obesity) and for each age group 1 to 12yrs (post-hoc Tukey Kramer/Dunnett's C; alpha = 0.05).
Results
Mean walking velocity was 0.95 +/- 0.25 m/s with no differences between normal-weight, overweight or obese children (p = 0.0841). Results show higher foot contact area, arch index, peak pressure and force time integral in overweight and obese children (p< 0.001). Obese children showed the 1.48-fold (1 year-old) to 3.49-fold (10 year-old) midfoot loading (FTI) compared to normal-weight.
Conclusion
Additional body mass leads to higher overall load, with disproportional impact on the midfoot area and longitudinal foot arch showing characteristic foot loading patterns. Already the feet of one and two year old children are significantly affected. Childhood overweight and obesity is not compensated by the musculoskeletal system. To avoid excessive foot loading with potential risk of discomfort or pain in childhood, prevention strategies should be developed and validated for children with a high body mass index and functional changes in the midfoot area. The presented plantar pressure values could additionally serve as reference data to identify suspicious foot loading patterns in children.
DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.
Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N′-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of −22 to −71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures.
Catalytic amounts of a weak base are sufficient to induce the decomposition of anthracene endoperoxides to anthraquinone. The mechanism has been elucidated by isolation of intermediates in combination with DFT calculations. The whole process is suitable for the convenient generation of hydrogen peroxide under very mild conditions.
A multi-reference study of the byproduct formation for a ring-closed dithienylethene photoswitch
(2015)
Photodriven molecular switches are sometimes hindered in their performance by forming byproducts which act as dead ends in sequences of switching cycles, leading to rapid fatigue effects. Understanding the reaction pathways to unwanted byproducts is a prerequisite for preventing them. This article presents a study of the photochemical reaction pathways for byproduct formation in the photochromic switch 1,2-bis-(3-thienyl)-ethene. Specifically, using single- and multi-reference methods the post-deexcitation reaction towards the byproduct in the electronic ground state S0 when starting from the S1–S0 conical intersection (CoIn), is considered in detail. We find an unusual low-energy pathway, which offers the possibility for the formation of a dyotropic byproduct. Several high-energy pathways can be excluded with high probability.
Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides
(2015)
The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.
NaYF4:Yb:Er nanoparticles (UCNP) were synthesized under mild experimental conditions to obtain a pure cubic lattice. Upon annealing at different temperatures up to Tan = 700 °C phase transitions to the hexagonal phase and back to the cubic phase were induced. The UCNP materials obtained for different Tan were characterized with respect to the lattice phase using standard XRD and Raman spectroscopy as well as steady state and time resolved upconversion luminescence. The standard techniques showed that for the annealing temperature range 300 °C < Tan < 600 °C the hexagonal lattice phase was dominant. For Tan < 300 °C hardly any change in the lattice phase could be deduced, whereas for Tan > 600 °C a back transfer to the α-phase was observed. Complementarily, the luminescence upconversion properties of the annealed UCNP materials were characterized in steady state and time resolved luminescence measurements. Distinct differences in the upconversion luminescence intensity, the spectral intensity distribution and the luminescence decay kinetics were found for the cubic and hexagonal lattice phases, respectively, corroborating the results of the standard analytical techniques used. In laser power dependent measurements of the upconversion luminescence intensity it was found that the green (G1, G2) and red (R) emission of Er3+ showed different effects of Tan on the number of required photons reflecting the differences in the population routes of different energy levels involved. Furthermore, the intensity ratio of Gfull/R is highly effected by the laser power only when the β-phase is present, whereas the G1/G2 intensity ratio is only slightly effected regardless of the crystal phase. Moreover, based on different upconversion luminescence kinetics characteristics of the cubic and hexagonal phase time-resolved area normalized emission spectra (TRANES) proved to be a very sensitive tool to monitor the phase transition between cubic and hexagonal phases. Based on the TRANES analysis it was possible to resolve the lattice phase transition in more detail for 200 °C < Tan < 300 °C, which was not possible with the standard techniques.
Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale
(2015)
In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.
What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer–surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sc—defining the adsorption–desorption transition—are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sc for the concave interfaces versus the Debye screening length 1/k and the extent of confinement a for these three interfaces for small ka values. For large ka the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/k. We also rationalize how sc(k) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption—the effect often hard to tackle theoretically—putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids.
The phase behavior of an amphiphilic block copolymer based on a poly(aspartic acid) hydrophilic block and a poly(n-butyl acrylate) hydrophobic block was investigated at the air–water and air–buffer interface. The polymer forms stable monomolecular films on both subphases. At low pH, the isotherms exhibit a plateau. Compression–expansion experiments and infrared reflection absorption spectroscopy suggest that the plateau is likely due to the formation of polymer bi- or multilayers. At high pH the films remain intact upon compression and no multilayer formation is observed. Furthermore, the mineralization of calcium phosphate beneath the monolayer was studied at different pH. The pH of the subphase and thus the polymer charge strongly affects the phase behavior of the film and the mineral formation. After 4 h of mineralization at low pH, atomic force microscopy shows smooth mineral films with a low roughness. With increasing pH the mineral films become inhomogeneous and the roughness increases. Transmission electron microscopy confirms this: at low pH a few small but uniform particles form whereas particles grown at higher pH are larger and highly agglomerated. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirm the formation of calcium phosphate. The levels of mineralization are higher in samples grown at high pH.
Verdun 1916
(2016)
Mehrfachkrise und Populismus
(2016)
Der Aufsatz umreißt die Wirkung von Averroes’ Bearbeitung der aristotelischen ‚Poetik‘ als argumentativer Disziplin. Beginnend mit Al-Farabi und Al-Gazali im zehnten Jahrhundert wird die ‚Poetik‘ den logischen Disziplinen des ‚Organon‘ zugerechnet. Während die Theorie eines ‚poetischen Syllogismus‘ nicht rezipiert worden ist, wurde der argumentative Status der Dichtung vom zwölften Jahrhundert an auch im lateinischen Westen bekannt. Mit unterschiedlichen Begründungen übernahmen Dominicus Gundissalinus, Vincenz von Beauvais, Albertus Magnus, Roger Bacon und Thomas von Aquin die Klassifizierung der Poetik als argumentative Disziplin. Am Ende des Aufsatzes steht ein Ausblick auf Coluccio Salutatis ‚De laboribus Herculis‘ und die humanistische Rezeption dieser Tradition.
Der Aufsatz zeigt, dass es sich bei der averroischen Bearbeitung der aristotelischen ‚Poetik‘ um eine in sich konsistente Theorie der Dichtung handelt, die allerdings mit der aristotelischen Konzeption der Dichtung nur wenig zu tun hat. Ausgehend von der Übersetzung von ‚Tragödie‘ und ‚Komödie‘ mit ‚Lob‘ und ‚Tadel‘ entwickelt Averroes einen Begriff von Dichtung als moralphilosophisches Argument zum Lob der Tugend und zum Tadel des Lasters. Im Mittelpunkt steht die Interpretation des aristotelischen Begriffs der mimesis als similitudo, das heißt als Gleichnis. Als gleichnishaftes Argument ist Dichtung nur graduell von anderen argumentativen Formen wie der demonstrativen Logik und der Rhetorik unterschieden.
Die „Poetica“ Tommaso Campanellas ist Ausdruck einer starken Rationalisierung und didaktischer Instrumentalisierung der Dichtung. Diese Rationalisierung kann als Reaktion auf die Inspirationstheorien von Marsilio Ficino und Pietro Pomponazzi erklärt werden, die beide (mit je ganz unterschiedlichen Begründungen) den poetischen Enthusiasmus neben die Offenbarungen des Propheten gestellt und damit den ausschließlichen Offenbarungsanspruch der Prophetie herausgefordert hatten.