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Communicating location-specific information to pedestrians is a challenging task which can be aided by user-friendly digital technologies. In this paper, landmark visibility analysis, as a means for developing more usable pedestrian navigation systems, is discussed. Using an algorithmic framework for image-based 3D analysis, this method integrates a 3D city model with identified landmarks and produces raster visibility layers for each one. This output enables an Android phone prototype application to indicate the visibility of landmarks from the user's actual position. Tested in the field, the method achieves sufficient accuracy for the context of use and improves navigation efficiency and effectiveness.
Proposing relevant perturbations to biological signaling networks is central to many problems in biology and medicine because it allows for enabling or disabling certain biological outcomes. In contrast to quantitative methods that permit fine-grained (kinetic) analysis, qualitative approaches allow for addressing large-scale networks. This is accomplished by more abstract representations such as logical networks. We elaborate upon such a qualitative approach aiming at the computation of minimal interventions in logical signaling networks relying on Kleene's three-valued logic and fixpoint semantics. We address this problem within answer set programming and show that it greatly outperforms previous work using dedicated algorithms.
This study presents results from a cross-modal priming experiment investigating inflected verb forms of German. A group of late learners of German with Russian as their native language (L1) was compared to a control group of German L1 speakers. The experiment showed different priming patterns for the two participant groups. The L1 German data yielded a stem-priming effect for inflected forms involving regular affixation and a partial priming effect for irregular forms irrespective of stem allomorphy. By contrast, the data from the late bilinguals showed reduced priming effects for both regular and irregular forms. We argue that late learners rely more on lexically stored inflected word forms during word recognition and less on morphological parsing than native speakers.
Previous research has shown that high phonotactic frequencies
facilitate the production of regularly inflected verbs in English-learning
children with specific language impairment (SLI) but not with typical
development (TD). We asked whether this finding can be replicated
for German, a language with a much more complex inflectional
verb paradigm than English. Using an elicitation task, the production
of inflected nonce verb forms (3 rd person singular with -t suffix)
with either high- or low-frequency subsyllables was tested in
sixteen German-learning children with SLI (ages 4;1–5 ;1), sixteen
TD-children matched for chronological age (CA) and fourteen TD-
children matched for verbal age (VA) (ages 3;0–3 ;11). The findings
revealed that children with SLI, but not CA- or VA-children, showed
differential performance between the two types of verbs, producing
more inflectional errors when the verb forms resulted in low-frequency
subsyllables than when they resulted in high-frequency subsyllables,
replicating the results from English-learning children.
The course timetabling problem can be generally defined as the task of assigning a number of lectures to a limited set of timeslots and rooms, subject to a given set of hard and soft constraints. The modeling language for course timetabling is required to be expressive enough to specify a wide variety of soft constraints and objective functions. Furthermore, the resulting encoding is required to be extensible for capturing new constraints and for switching them between hard and soft, and to be flexible enough to deal with different formulations. In this paper, we propose to make effective use of ASP as a modeling language for course timetabling. We show that our ASP-based approach can naturally satisfy the above requirements, through an ASP encoding of the curriculum-based course timetabling problem proposed in the third track of the second international timetabling competition (ITC-2007). Our encoding is compact and human-readable, since each constraint is individually expressed by either one or two rules. Each hard constraint is expressed by using integrity constraints and aggregates of ASP. Each soft constraint S is expressed by rules in which the head is the form of penalty (S, V, C), and a violation V and its penalty cost C are detected and calculated respectively in the body. We carried out experiments on four different benchmark sets with five different formulations. We succeeded either in improving the bounds or producing the same bounds for many combinations of problem instances and formulations, compared with the previous best known bounds.
In various biological systems and small scale technological applications particles transiently bind to a cylindrical surface. Upon unbinding the particles diffuse in the vicinal bulk before rebinding to the surface. Such bulk-mediated excursions give rise to an effective surface translation, for which we here derive and discuss the dynamic equations, including additional surface diffusion. We discuss the time evolution of the number of surface-bound particles, the effective surface mean squared displacement, and the surface propagator. In particular, we observe sub- and superdiffusive regimes. A plateau of the surface mean-squared displacement reflects a stalling of the surface diffusion at longer times. Finally, the corresponding first passage problem for the cylindrical geometry is analysed.
This article expands our current knowledge about ministerial selection in coalition governments and analyses why ministerial candidates succeed in acquiring a cabinet position after general elections. It argues that political parties bargain over potential office-holders during government-formation processes, selecting future cabinet ministers from an emerging bargaining pool'. The article draws upon a new dataset comprising all ministrable candidates discussed by political parties during eight government-formation processes in Germany between 1983 and 2009. The conditional logit regression analysis reveals that temporal dynamics, such as the day she enters the pool, have a significant effect on her success in achieving a cabinet position. Other determinants of ministerial selection discussed in the existing literature, such as party and parliamentary expertise, are less relevant for achieving ministerial office. The article concludes that scholarship on ministerial selection requires a stronger emphasis for its endogenous nature in government-formation as well as the relevance of temporal dynamics in such processes.
OCP-Place, a cross-linguistically well-attested constraint against pairs of consonants with shared [place], is psychologically real. Studies have shown that the processing of words violating OCP-Place is inhibited. Functionalists assume that OCP arises as a consequence of low-level perception: a consonant following another with the same [place] cannot be faithfully perceived as an independent unit. If functionalist theories were correct, then lexical access would be inhibited if two homorganic consonants conjoin at word boundaries-a problem that can only be solved with lexical feedback.
Here, we experimentally challenge the functional account by showing that OCP-Place can be used as a speech segmentation cue during pre-lexical processing without lexical feedback, and that the use relates to distributions in the input.
In Experiment 1, native listeners of Dutch located word boundaries between two labials when segmenting an artificial language. This indicates a use of OCP-Labial as a segmentation cue, implying a full perception of both labials. Experiment 2 shows that segmentation performance cannot solely be explained by well-formedness intuitions. Experiment 3 shows that knowledge of OCP-Place depends on language-specific input: in Dutch, co-occurrences of labials are under-represented, but co-occurrences of coronals are not. Accordingly, Dutch listeners fail to use OCP-Coronal for segmentation.
Despite recent growth of research on the effects of prosocial media, processes underlying these effects are not well understood. Two studies explored theoretically relevant mediators and moderators of the effects of prosocial media on helping. Study 1 examined associations among prosocial- and violent-media use, empathy, and helping in samples from seven countries. Prosocial-media use was positively associated with helping. This effect was mediated by empathy and was similar across cultures. Study 2 explored longitudinal relations among prosocial-video-game use, violent-video-game use, empathy, and helping in a large sample of Singaporean children and adolescents measured three times across 2 years. Path analyses showed significant longitudinal effects of prosocial- and violent-video-game use on prosocial behavior through empathy. Latent-growth-curve modeling for the 2-year period revealed that change in video-game use significantly affected change in helping, and that this relationship was mediated by change in empathy.
The aim of the present study was to examine how different types of tracking— between-school streaming, within-school streaming, and course-by-course tracking—shape students’ mathematics self-concept. This was done in an internationally comparative framework using data from the Programme for International Student Assessment (PISA). After controlling for individual and track mean achievement, results indicated that generally for students in course-by-course tracking, high-track students had higher mathematics self-concepts and low-track students had lower mathematics self-concepts. For students in between-school and within-school streaming, the reverse pattern was found. These findings suggest a solution to the ongoing debate about the effects of tracking on students’ academic self-concept and suggest that the reference groups to which students compare themselves differ according to the type of tracking.
We report findings from psycholinguistic experiments investigating the detailed timing of processing morphologically complex words by proficient adult second (L2) language learners of English in comparison to adult native (L1) speakers of English. The first study employed the masked priming technique to investigate -ed forms with a group of advanced Arabic-speaking learners of English. The results replicate previously found L1/L2 differences in morphological priming, even though in the present experiment an extra temporal delay was offered after the presentation of the prime words.
The second study examined the timing of constraints against inflected forms inside derived words in English using the eye-movement monitoring technique and an additional acceptability judgment task with highly advanced Dutch L2 learners of English in comparison to adult L1 English controls. Whilst offline the L2 learners performed native-like, the eye-movement data showed that their online processing was not affected by the morphological constraint against regular plurals inside derived words in the same way as in native speakers. Taken together, these findings indicate that L2 learners are not just slower than native speakers in processing morphologically complex words, but that the L2 comprehension system employs real-time grammatical analysis (in this case, morphological information) less than the L1 system.
Background: Neuroenhancement (NE), the use of psychoactive substances in order to enhance a healthy individual's cognitive functioning from a proficient to an even higher level, is prevalent in student populations. According to the strength model of self-control, people fail to self-regulate and fall back on their dominant behavioral response when finite self-control resources are depleted. An experiment was conducted to test the hypothesis that ego-depletion will prevent students who are unfamiliar with NE from trying it.
Findings: 130 undergraduates, who denied having tried NE before (43% female, mean age = 22.76 +/- 4.15 years old), were randomly assigned to either an ego-depletion or a control condition. The dependent variable was taking an "energy-stick" (a legal nutritional supplement, containing low doses of caffeine, taurine and vitamin B), offered as a potential means of enhancing performance on the bogus concentration task that followed. Logistic regression analysis showed that ego-depleted participants were three times less likely to take the substance, OR = 0.37, p = .01.
Conclusion: This experiment found that trying NE for the first time was more likely if an individual's cognitive capacities were not depleted. This means that mental exhaustion is not predictive for NE in students for whom NE is not the dominant response. Trying NE for the first time is therefore more likely to occur as a thoughtful attempt at self-regulation than as an automatic behavioral response in stressful situations. We therefore recommend targeting interventions at this inter-individual difference. Students without previous reinforcing NE experience should be provided with information about the possible negative health outcomes of NE. Reconfiguring structural aspects in the academic environment (e.g. lessening workloads) might help to deter current users.
Background: Short lived, iteroparous animals in seasonal environments experience variable social and environmental conditions over their lifetime. Animals can be divided into those with a "young-of-the-year" life history (YY, reproducing and dying in the summer of birth) and an "overwinter" life history (OW, overwintering in a subadult state before reproducing next spring).
We investigated how behavioural patterns across the population were affected by season and sex, and whether variation in behaviour reflects the variation in life history patterns of each season. Applications of pace-of-life (POL) theory would suggest that long-lived OW animals are shyer in order to increase survival, and YY are bolder in order to increase reproduction. Therefore, we expected that in winter and spring samples, when only OW can be sampled, the animals should be shyer than in summer and autumn, when both OW and YY animals can be sampled. We studied common vole (Microtus arvalis) populations, which express typical, intra-annual density fluctuation. We captured a total of 492 voles at different months over 3 years and examined boldness and activity level with two standardised behavioural experiments.
Results: Behavioural variables of the two tests were correlated with each other. Boldness, measured as short latencies in both tests, was extremely high in spring compared to other seasons. Activity level was highest in spring and summer, and higher in males than in females.
Conclusion: Being bold in laboratory tests may translate into higher risk-taking in nature by being more mobile while seeking out partners or valuable territories. Possible explanations include asset-protection, with OW animals being rather old with low residual reproductive value in spring. Therefore, OW may take higher risks during this season. Offspring born in spring encounter a lower population density and may have higher reproductive value than offspring of later cohorts. A constant connection between life history and animal personality, as suggested by the POL theory, however, was not found. Nevertheless, correlations of traits suggest the existence of animal personalities. In conclusion, complex patterns of population dynamics, seasonal variation in life histories, and variability of behaviour due to asset-protection may cause complex seasonal behavioural dynamics in a population.
Background: Adaptive behavioural strategies promoting co-occurrence of competing species are known to result from a sympatric evolutionary past. Strategies should be different for indirect resource competition (exploitation, e.g., foraging and avoidance behaviour) than for direct interspecific interference (e.g., aggression, vigilance, and nest guarding). We studied the effects of resource competition and nest predation in sympatric small mammal species using semi-fossorial voles and shrews, which prey on vole offspring during their sensitive nestling phase. Experiments were conducted in caged outdoor enclosures. Focus common vole mothers (Microtus arvalis) were either caged with a greater white-toothed shrew (Crocidura russula) as a potential nest predator, with an herbivorous field vole (Microtus agrestis) as a heterospecific resource competitor, or with a conspecific resource competitor.
Results: We studied behavioural adaptations of vole mothers during pregnancy, parturition, and early lactation, specifically modifications of the burrow architecture and activity at burrow entrances. Further, we measured pre- and postpartum faecal corticosterone metabolites (FCMs) of mothers to test for elevated stress hormone levels. Only in the presence of the nest predator were prepartum FCMs elevated, but we found no loss of vole nestlings and no differences in nestling body weight in the presence of the nest predator or the heterospecific resource competitor. Although the presence of both the shrew and the field vole induced prepartum modifications to the burrow architecture, only nest predators caused an increase in vigilance time at burrow entrances during the sensitive nestling phase.
Conclusion: Voles displayed an adequate behavioural response for both resource competitors and nest predators. They modified burrow architecture to improve nest guarding and increased their vigilance at burrow entrances to enhance offspring survival chances. Our study revealed differential behavioural adaptations to resource competitors and nest predators.
Movement of organisms is one of the key mechanisms shaping biodiversity, e.g. the distribution of genes, individuals and species in space and time. Recent technological and conceptual advances have improved our ability to assess the causes and consequences of individual movement, and led to the emergence of the new field of ‘movement ecology’. Here, we outline how movement ecology can contribute to the broad field of biodiversity research, i.e. the study of processes and patterns of life among and across different scales, from genes to ecosystems, and we propose a conceptual framework linking these hitherto largely separated fields of research. Our framework builds on the concept of movement ecology for individuals, and demonstrates its importance for linking individual organismal movement with biodiversity. First, organismal movements can provide ‘mobile links’ between habitats or ecosystems, thereby connecting resources, genes, and processes among otherwise separate locations. Understanding these mobile links and their impact on biodiversity will be facilitated by movement ecology, because mobile links can be created by different modes of movement (i.e., foraging, dispersal, migration) that relate to different spatiotemporal scales and have differential effects on biodiversity. Second, organismal movements can also mediate coexistence in communities, through ‘equalizing’ and ‘stabilizing’ mechanisms. This novel integrated framework provides a conceptual starting point for a better understanding of biodiversity dynamics in light of individual movement and space-use behavior across spatiotemporal scales. By illustrating this framework with examples, we argue that the integration of movement ecology and biodiversity research will also enhance our ability to conserve diversity at the genetic, species, and ecosystem levels.
Background
Appearance-related social pressure plays an important role in the development of a negative body image and self-esteem as well as severe mental disorders during adolescence (e.g. eating disorders, depression). Identifying who is particularly affected by social pressure can improve targeted prevention and intervention, but findings have either been lacking or controversial. Thus the aim of this study is to provide a detailed picture of gender, weight, and age-related variations in the perception of appearance-related social pressure by peers and parents.
Methods
1112 German students between grades 7 and 9 (mean age: M = 13.38, SD = .81) filled in the Appearance-Related Social Pressure Questionnaire (German: FASD), which considers different sources (peers, parents) as well as various kinds of social pressure (e.g. teasing, modeling, encouragement).
Results
Girls were more affected by peer pressure, while gender differences in parental pressure seemed negligible. Main effects of grade-level suggested a particular increase in indirect peer pressure (e.g. appearance-related school and class norms) from early to middle adolescence. Boys and girls with higher BMI were particularly affected by peer teasing and exclusion as well as by parental encouragement to control weight and shape.
Conclusion
The results suggest that preventive efforts targeting body concerns and disordered eating should bring up the topic of appearance pressure in a school-based context and should strengthen those adolescents who are particularly at risk - in our study, girls and adolescents with higher weight status. Early adolescence and school transition appear to be crucial periods for these efforts. Moreover, the comprehensive assessment of appearance-related social pressure appears to be a fruitful way to further explore social risk-factors in the development of a negative body image.
Background: The use of psychoactive substances to neuroenhance cognitive performance is prevalent. Neuroenhancement (NE) in everyday life and doping in sport might rest on similar attitudinal representations, and both behaviors can be theoretically modeled by comparable means-to-end relations (substance-performance). A behavioral (not substance-based) definition of NE is proposed, with assumed functionality as its core component. It is empirically tested whether different NE variants (lifestyle drug, prescription drug, and illicit substance) can be regressed to school stressors.
Findings: Participants were 519 students (25.8 +/- 8.4 years old, 73.1% female). Logistic regressions indicate that a modified doping attitude scale can predict all three NE variants. Multiple NE substance abuse was frequent. Overwhelming demands in school were associated with lifestyle and prescription drug NE.
Conclusions: Researchers should be sensitive for probable structural similarities between enhancement in everyday life and sport and systematically explore where findings from one domain can be adapted for the other. Policy makers should be aware that students might misperceive NE as an acceptable means of coping with stress in school, and help to form societal sensitivity for the topic of NE among our younger ones in general.
Background
Natural accessions of Arabidopsis thaliana are a well-known system to measure levels of intraspecific genetic variation. Leaf starch content correlates negatively with biomass. Starch is synthesized by the coordinated action of many (iso)enzymes. Quantitatively dominant is the repetitive transfer of glucosyl residues to the non-reducing ends of α-glucans as mediated by starch synthases. In the genome of A. thaliana, there are five classes of starch synthases, designated as soluble starch synthases (SSI, SSII, SSIII, and SSIV) and granule-bound synthase (GBSS). Each class is represented by a single gene. The five genes are homologous in functional domains due to their common origin, but have evolved individual features as well. Here, we analyze the extent of genetic variation in these fundamental protein classes as well as possible functional implications on transcript and protein levels.
Findings
Intraspecific sequence variation of the five starch synthases was determined by sequencing the entire loci including promoter regions from 30 worldwide distributed accessions of A. thaliana. In all genes, a considerable number of nucleotide polymorphisms was observed, both in non-coding and coding regions, and several amino acid substitutions were identified in functional domains. Furthermore, promoters possess numerous polymorphisms in potentially regulatory cis-acting regions. By realtime experiments performed with selected accessions, we demonstrate that DNA sequence divergence correlates with significant differences in transcript levels.
Conclusions
Except for AtSSII, all starch synthase classes clustered into two or three groups of haplotypes, respectively. Significant difference in transcript levels among haplotype clusters in AtSSIV provides evidence for cis-regulation. By contrast, no such correlation was found for AtSSI, AtSSII, AtSSIII, and AtGBSS, suggesting trans-regulation. The expression data presented here point to a regulation by common trans-regulatory transcription factors which ensures a coordinated action of the products of these four genes during starch granule biosynthesis. The apparent cis-regulation of AtSSIV might be related to its role in the initiation of de novo biosynthesis of granules.
Introduction: We examined patterns of genetic divergence in 26 Mediterranean populations of the semi-terrestrial beachflea Orchestia montagui using mitochondrial (cytochrome oxidase subunit I), microsatellite (eight loci) and allozymic data. The species typically forms large populations within heaps of dead seagrass leaves stranded on beaches at the waterfront. We adopted a hierarchical geographic sampling to unravel population structure in a species living at the sea-land transition and, hence, likely subjected to dramatically contrasting forces.
Results: Mitochondrial DNA showed historical phylogeographic breaks among Adriatic, Ionian and the remaining basins (Tyrrhenian, Western and Eastern Mediterranean Sea) likely caused by the geological and climatic changes of the Pleistocene. Microsatellites (and to a lesser extent allozymes) detected a further subdivision between and within the Western Mediterranean and the Tyrrhenian Sea due to present-day processes. A pattern of isolation by distance was not detected in any of the analyzed data set.
Conclusions: We conclude that the population structure of O. montagui is the result of the interplay of two contrasting forces that act on the species population genetic structure. On one hand, the species semi-terrestrial life style would tend to determine the onset of local differences. On the other hand, these differences are partially counter-balanced by passive movements of migrants via rafting on heaps of dead seagrass leaves across sites by sea surface currents. Approximate Bayesian Computations support dispersal at sea as prevalent over terrestrial regionalism.
The PSM-leadership fit
(2013)
This article examines the use of performance information by public managers. It conceptualizes purposeful data use as a type of extra-role behaviour which requires additional effort on the part of the managers and which is not extrinsically rewarded. The article sheds light on one potential antecedent of performance information use – the motivation of the users. It argues that we can observe high levels of data use if managers driven by public service motivation (PSM) work under transformational leaders. Using a needs-supply perspective on supervisors and followers we suggest that there is a PSM-leadership fit which fosters the performance of this extra-role behaviour. The article is based on data from German local government and its findings contribute to the literatures on PSM as well as on performance management.
We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.
Derivatization of fullerene (C60) with branched aliphatic chains softens C60-based materials and enables the formation of thermotropic liquid crystals and room temperature nonvolatile liquids. This work demonstrates that by carefully tuning parameters such as type, number and substituent position of the branched chains, liquid crystalline C60 materials with mesophase temperatures suited for photovoltaic cell fabrication and room temperature nonvolatile liquid fullerenes with tunable viscosity can be obtained. In particular, compound 1, with branched chains, exhibits a smectic liquid crystalline phase extending from 84 °C to room temperature. Analysis of bulk heterojunction (BHJ) organic solar cells with a ca. 100 nm active layer of compound 1 and poly(3-hexylthiophene) (P3HT) as an electron acceptor and an electron donor, respectively, reveals an improved performance (power conversion efficiency, PCE: 1.6 ± 0.1%) in comparison with another compound, 10 (PCE: 0.5 ± 0.1%). The latter, in contrast to 1, carries linear aliphatic chains and thus forms a highly ordered solid lamellar phase at room temperature. The solar cell performance of 1 blended with P3HT approaches that of PCBM/P3HT for the same active layer thickness. This indicates that C60 derivatives bearing branched tails are a promising class of electron acceptors in soft (flexible) photovoltaic devices.
A water soluble fluorescent polymer as a dual colour sensor for temperature and a specific protein
(2013)
We present two thermoresponsive water soluble copolymers prepared via free radical statistical copolymerization of N-isopropylacrylamide (NIPAm) and of oligo(ethylene glycol) methacrylates (OEGMAs), respectively, with a solvatochromic 7-(diethylamino)-3-carboxy-coumarin (DEAC)- functionalized monomer. In aqueous solutions, the NIPAm-based copolymer exhibits characteristic changes in its fluorescence profile in response to a change in solution temperature as well as to the presence of a specific protein, namely an anti-DEAC antibody. This polymer emits only weakly at low temperatures, but exhibits a marked fluorescence enhancement accompanied by a change in its emission colour when heated above its cloud point. Such drastic changes in the fluorescence and absorbance spectra are observed also upon injection of the anti-DEAC antibody, attributed to the specific binding of the antibody to DEAC moieties. Importantly, protein binding occurs exclusively when the polymer is in the well hydrated state below the cloud point, enabling a temperature control on the molecular recognition event. On the other hand, heating of the polymer–antibody complexes releases a fraction of the bound antibody. In the presence of the DEAC-functionalized monomer in this mixture, the released antibody competitively binds to the monomer and the antibody-free chains of the polymer undergo a more effective collapse and inter-aggregation. In contrast, the emission properties of the OEGMA-based analogous copolymer are rather insensitive to the thermally induced phase transition or to antibody binding. These opposite behaviours underline the need for a carefully tailored molecular design of responsive polymers aimed at specific applications, such as biosensing.
Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as “activation agents” with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt%). In addition, this “induced carbonization” and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.
We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.
Continuous synthesis of pyridocarbazoles and initial photophysical and bioprobe characterization
(2013)
Pyridocarbazoles when ligated to transition metals yield high affinity kinase inhibitors. While batch photocyclizations enable the synthesis of these heterocycles, the non-oxidative Mallory reaction only provides modest yields and difficult to purify mixtures. We demonstrate here that a flow-based Mallory cyclization provides superior results and enables observation of a clear isobestic point. The flow method allowed us to rapidly synthesize ten pyridocarbazoles and for the first time to document their interesting photophysical attributes. Preliminary characterization reveals that these molecules might be a new class of fluorescent bioprobe.
Calcium phosphate nanofibers with a diameter of only a few nanometers and a cotton-ball-like aggregate morphology have been reported several times in the literature. Although fiber formation seems reproducible in a variety of conditions, the crystal structure and chemical composition of the fibers have been elusive. Using scanning transmission electron microscopy, low dose electron (nano)diffraction, energy-dispersive X-ray spectroscopy, and energy-filtered transmission electron microscopy, we have assigned crystal structures and chemical compositions to the fibers. Moreover, we demonstrate that the mineralization process yields true polymer/calcium phosphate hybrid materials where the block copolymer template is closely associated with the calcium phosphate.
A polymer analogous reaction for the formation of imidazolium and NHC based porous polymer networks
(2013)
A polymer analogous reaction was carried out to generate a porous polymeric network with N-heterocyclic carbenes (NHC) in the polymer backbone. Using a stepwise approach, first a polyimine network is formed by polymerization of the tetrafunctional amine tetrakis(4-aminophenyl)methane. This polyimine network is converted in the second step into polyimidazolium chloride and finally to a polyNHC network. Furthermore a porous Cu(II)-coordinated polyNHC network can be generated. Supercritical drying generates polymer networks with high permanent surface areas and porosities which can be applied for different catalytic reactions. The catalytic properties were demonstrated for example in the activation of CO2 or in the deoxygenation of sulfoxides to the corresponding sulfides.
4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4’-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.
Under standard conditions the cross metathesis of allyl alcohols and methyl acrylate is accompanied by the formation of ketones, resulting from uncontrolled and undesired double bond isomerization. By conducting the CM in the presence of phenol, the catalyst loading and the reaction time required for quantiative conversion can be reduced, and isomerization can be suppressed. On the other hand, consecutive isomerization can be deliberately promoted by evaporating excess methyl acrylate after completing cross metathesis and by adding a base or silane as chemical triggers.
We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.
Intracellular photoactivation of caged cGMP induces myosin II and actin responses in motile cells
(2013)
Cyclic GMP (cGMP) is a ubiquitous second messenger in eukaryotic cells. It is assumed to regulate the association of myosin II with the cytoskeleton of motile cells. When cells of the social amoeba Dictyostelium discoideum are exposed to chemoattractants or to increased osmotic stress, intracellular cGMP levels rise, preceding the accumulation of myosin II in the cell cortex. To directly investigate the impact of intracellular cGMP on cytoskeletal dynamics in a living cell, we released cGMP inside the cell by laser-induced photo-cleavage of a caged precursor. With this approach, we could directly show in a live cell experiment that an increase in intracellular cGMP indeed induces myosin II to accumulate in the cortex. Unexpectedly, we observed for the first time that also the amount of filamentous actin in the cell cortex increases upon a rise in the cGMP concentration, independently of cAMP receptor activation and signaling. We discuss our results in the light of recent work on the cGMP signaling pathway and suggest possible links between cGMP signaling and the actin system.
With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
The time-dependent approach to electronic spectroscopy, as popularized by Heller and coworkers in the 1980's, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption, emission and resonance Raman spectra of several diamondoids. Two-state models, the harmonic and the Condon approximations, are used for the calculations, making them easily applicable to larger molecules. The method is applied to nine pristine lower and higher diamondoids: adamantane, diamantane, triamantane, and three isomers each of tetramantane and pentamantane. We also consider a hybrid species “Dia = Dia” – a shorthand notation for a recently synthesized molecule comprising two diamantane units connected by a C[double bond, length as m-dash]C double bond. We resolve and interpret trends in optical and vibrational properties of these molecules as a function of their size, shape, and symmetry, as well as effects of “blending” with sp2-hybridized C-atoms. Time-dependent correlation functions facilitate the computations and shed light on the vibrational dynamics following electronic transitions.
We consider diffusion processes with a spatially varying diffusivity giving rise to anomalous diffusion. Such heterogeneous diffusion processes are analysed for the cases of exponential, power-law, and logarithmic dependencies of the diffusion coefficient on the particle position. Combining analytical approaches with stochastic simulations, we show that the functional form of the space-dependent diffusion coefficient and the initial conditions of the diffusing particles are vital for their statistical and ergodic properties. In all three cases a weak ergodicity breaking between the time and ensemble averaged mean squared displacements is observed. We also demonstrate a population splitting of the time averaged traces into fast and slow diffusers for the case of exponential variation of the diffusivity as well as a particle trapping in the case of the logarithmic diffusivity. Our analysis is complemented by the quantitative study of the space coverage, the diffusive spreading of the probability density, as well as the survival probability.
A Co(II)–imidazolate-4-amide-5-imidate based MOF, IFP-5, is synthesized by using an imidazolate anion-based novel ionic liquid as a linker precursor under solvothermal conditions. IFP-5 shows significant amounts of gas (N2, CO2, CH4 and H2) uptake capacities. IFP-5 exhibits an independent high spin Co(II) centre and antiferromagnetic coupling.
A rare example of in situ linker generation with the formation of soft porous Zn- and Co-MOFs (IFP-9 and -10, respectively) is reported. The flexible ethoxy groups of IFP-9 and -10 protrude into the 1D hexagonal channels. The gas-sorption behavior of both materials for H2, CO2 and CH4 showed wide hysteretic isotherms, typical for MOFs having a flexible substituent which can give rise to a gate effect.
This article presents the results of a study on the interpretation and acceptance of adjectival resultatives of German children between 6 and 9 years of age and adults. These results brought to light significant differences, due to age, in the interpretation and acceptance of these resultatives, that is to say, sentences with an adjective in the final position. The youngest participants were prone to accept ungrammatical sentences by assigning a resultative meaning. The ungrammaticality of the sentences in question was not due to semantic inconsistencies but to violations of the selectional properties of verbs, as for instance in *die Kinder erschrecken die Katze ängstlich ‘the children frighten the cat scared’. In contrast, the adults rejected or amended those sentences. The conclusion is (a) that the children seemed to rely on the sentence structure as a primary cue to compute the meaning of an utterance and (b) that, in contrast with adults, the youngest children in particular had not yet learned the relevant semantic properties of verbs that determine the selectional restrictions and thus the syntactic options of verbs. This means that differences in interpretation and acceptance of sentences are due to differences in knowledge of semantic verb properties between adults and children. The relevant semantic knowledge increases in gradual stages during language acquisition.
In this article, it will be argued that the concept of functional layering – an extension of Hopper’s (1991) concept of layering – can be fruitfully applied to understand the mechanisms behind the sometimes large and messy looking synchronic picture of diverse meanings which one and the same construction can fulfill at a particular point in time. The concept will be used to account for the meaning spectrum of the present-day English progressive, which, it will be argued, no monosemic approach to date can account for. Taking a look at the diachrony of the construction will help to reveal that the various “exceptions” found in the use of the progressive can be understood as reflections of different stages in its development. Older, less grammaticalized or less well-defined usage patterns thus often survive in certain restricted niches next to the newer, more grammaticalized or more clear-cut functions, representing different diachronic layers. In addition to this diachronic motivation for synchronic meaning variety, the article will also address the crucial question of how a present-day hearer of a progressive form is able to decode the specific meaning intended by the speaker based on contextual clues. The article ends with some suggestions for further applications of the concept of functional layering.
Deep into the second half of the twentieth century the traditionalist definition of India as a country of villages remained dominant in official political rhetoric as well as cultural production. In the past two decades or so, this ruralist paradigm has been effectively superseded by a metropolitan imaginary in which the modern, globalised megacity increasingly functions as representative of India as a whole. Has the village, then, entirely vanished from the cultural imaginary in contemporary India? Addressing economic practices from upper-class consumerism to working-class family support strategies, this paper attempts to trace how ‘the village’ resurfaces or survives as a cultural reference point in the midst of the urban.
Filming illegals
(2013)
Introduction
(2013)
One of the central questions in psycholinguistic is understanding whether and how prosodic phrase boundaries are used to resolve syntactic ambiguities in sentence processing. The present work aimed to answer both, first, the effects of φ- and ι-boundaries on syntactic ambiguity resolution, and second, how the prosodic correlates of the auditory input are taken for the phonetic-phonology mapping in order to attain a meaningful sentence interpretation.
With regard to the first aim, we investigated locally syntactic ambiguities involving either φ- or ι-phrase boundaries in German and the structural preference that listeners have, based on the prosodic content. The experiments described in this work show that German listeners exploit both types of prosodic phrase boundaries to resolve local syntactic ambiguities, that however, their disambiguation altered by the presence or absence of prosodic cues correlated with the corresponding boundary. Specifically, the perception data revealed that the phonetically measured prosodic correlates of each prosodic boundary such as pitch accents, boundary tones, deaccentuation and durational properties do not contribute to ambiguity resolution in equal measure. Rather, it is the case that listeners rely primarily on prefinal lengthening as a correlate of phrasing in the vicinity of φ-phrase boundaries, while at the level of the ι-phrase boundary, boundary tones serve as phrasal cues. This way the results of the present work take account of the as yet missing information on individual contributions of prosodic correlates on listeners’ disambiguation of syntactically ambiguous sentences in German. It further implies that the question of how German listeners resolve syntactic ambiguities cannot simply be attributed to the presence or absence of prosodic correlates. The interpretation of the phrasal structure rather depends on a more general picture of cohesion between prosodic correlates and prosodic boundary sizes.
With respect to the second aim, the processing models proposed in the present work describe a specific phonetics-phonology mapping in the vicinity of both phrase boundaries. It is assumed that auditory sentence processing proceeds in several successively organized steps, during which listeners transform overt phonetic forms into language specific abstract surface forms. This process is referred to as phonetics-phonology mapping in the present work. Perceptual evidence resulting from the experiments of the present work suggest that the phonetics-phonology mapping is guided by the above mentioned boundary related prosodic correlates. The resulting abstract phonological structure is subjected to the syntax-prosody mapping, in turn. The outcome of the presented perception experiments are modulated in an Optimality-Theoretic framework. The offered OT-models are grounded on the assumption that single prosodic correlates are used by listeners as a signal to syntax in sentence processing. This is in line with studies arguing that the prosodic phrase structure determines the syntactic parse (Cutler et al., 1997; Warren et al., 1995; Pynte & Prieur, 1996; Snedeker & Trueswell, 2003; Kjelgaard & Speer, 1999), to name just a few.
Rhythm is a temporal and systematic organization of acoustic events in terms of prominence, timing and grouping, helping to structure our most basic experiences, such as body movement, music and speech. In speech, rhythm groups auditory events, e.g., sounds and pauses, together into words, making their boundaries acoustically prominent and aiding word segmentation and recognition by the hearer. After word recognition, the hearer is able to retrieve word meaning form his mental lexicon, integrating it with information from other linguistic domains, such as semantics, syntax and pragmatics, until comprehension is achieved. The importance of speech rhythm, however, is not restricted to word segmentation and recognition only. Beyond the word level rhythm continues to operate as an organization device, interacting with different linguistic domains, such as syntax and semantics, and grouping words into larger prosodic constituents, organized in a prosodic hierarchy. This dissertation investigates the function of speech rhythm as a sentence segmentation device during syntactic ambiguity processing, possible limitations on its use, i.e., in the context of second language processing, and its transferability as cognitive skill to the music domain.
Inhibition, attentional control, and causes of forgetting in working memory: a formal approach
(2013)
In many cognitive activities, the temporary maintenance and manipulation of mental objects is a necessary step in order to reach a cognitive goal. Working memory has been regarded as the process responsible for those cognitive activities. This thesis addresses the question: what limits working-memory capacity (WMC)? A question that still remains controversial (Barrouillet & Camos, 2009; Lewandowsky, Oberauer, & Brown, 2009). This study attempted to answer this question by proposing that the dynamics between the causes of forgetting and the processes helping the maintenance, and the manipulation of the memoranda are the key aspects in understanding the limits of WMC.
Chapter 1 introduced key constructs and the strategy to examine the dynamics between inhibition, attentional control, and the causes of forgetting in working memory.
The study in Chapter 2 tested the performance of children, young adults, and old adults in a working-memory updating-task with two conditions: one condition included go steps and the other condition included go, and no-go steps. The interference model (IM; Oberauer & Kliegl, 2006), a model proposing interference-related mechanisms as the main cause of forgetting was used to simultaneously fit the data of these age groups. In addition to the interference-related parameters reflecting interference by feature overwriting and interference by confusion, and in addition to the parameters reflecting the speed of processing, the study included a new parameter that captured the time for switching between go steps and no-go steps. The study indicated that children and young adults were less susceptible than old adults to interference by feature overwriting; children were the most susceptible to interference by confusion, followed by old adults and then by young adults; young adults presented the higher rate of processing, followed by children and then by old adults; and young adults were the fastest group switching from go steps to no-go steps.
Chapter 3 examined the dynamics between causes of forgetting and the inhibition of a prepotent response in the context of three formal models of the limits of WMC: A resources model, a decay-based model, and three versions of the IM. The resources model was built on the assumption that a limited and shared source of activation for the maintenance and manipulation of the objects underlies the limits of WMC. The decay model assumes that memory traces of the working-memory objects decay over time if they are not reactivated via different mechanisms of maintenance. The IM, already described, proposes that interference-related mechanisms explain the limits of WMC. In two experiments and in a reanalysis of data of the second experiment, one version of the IM received more statistical support from the data. This version of the IM proposes that interference by feature overwriting and interference by confusion are the main factors underlying the limits of WMC. In addition, the model suggests that experimental conditions involving the inhibition of a prepotent response reduce the speed of processing and promotes the involuntary activation of irrelevant information in working memory.
Chapter 4 summed up Chapter 2 and 3 and discussed their findings and presented how this thesis has provided evidence of interference-related mechanisms as the main cause of forgetting, and it has attempted to clarify the role of inhibition and attentional control in working memory. With the implementation of formal models and experimental manipulations in the framework of nonlinear mixed models the data offered explanations of causes of forgetting and the role of inhibition in WMC at different levels: developmental effects, aging effects, effects related to experimental manipulations and individual differences in these effects. Thus, the present approach afforded a comprehensive view of a large number of factors limiting WMC.
This dissertation is about factors that contribute to the surface forms of tones in connected speech in Akan. Akan is an African tone language, which is spoken in Ghana. It has two level tones (low and high), automatic and non-automatic downstep. Downstep is the major factor that influences the surface forms of tones. The thesis shows that downstep is caused by declination. It is argued that declination is an intonational property of Akan, which serves to signal coherence. A phonological representation using a high and a low register tone, associating to the left and right edge of an intonational phrase (IP), respectively, is proposed. Declination/downstep is modelled using a (phonetic) pitch implementation algorithm (Liberman & Pierrehumbert, 1984). An innovative application of the algorithm is presented, which naturally captures the relation between declination and downstep in Akan. Another important factor is the prosodic manifestation of sentence level pragmatic meanings, such as sentence mode and focus. Regarding the former, the thesis shows that a post-lexical low tone, which associates with the right edge of an IP, signals interrogativity. Additionally, lexical tones in Yes – No questions are realized in a higher pitch register, which does not lead to a reduction of declination. It is claimed that the higher register is not part of the phonological representation in Akan, but that it emerges at the phonetic level to compensate for the ‘unnatural’ form of the question morpheme and to satisfy the Frequency code (Gussenhoven, 2002; 2004). An extension of Rialland’s (2007) typology in terms of a new category called “low tense” question prosody is proposed. Concerning focus marking, it is argued that the use of the morpho-syntactic focus marking strategy is related to extra grammatical factors, such as hearer expectation, discourse expectability (Zimmermann, 2007) and emphasis (Hartmann, 2008). If a speaker of Akan wants to highlight a particular element in a sentence, in-situ, i.e. by means of prosody, the default prosodic structure is modified in such a way that the focused element forms its own phonological phrase (pP). If it is already contained in a pP, the boundary deliminating the focused element is enhanced (Féry, 2012). This restructuring/enhancement is accompanied by an interruption of the otherwise continuous melody due to insertion of a pause and/or a glottal stop. Beside declination and intonation, raising of H tones applies in Akan. H raising is analyzed as a local anticipatory planning effect, employed at the phonetic level, which enhances the perceptual distance between low and high tones. Low tones are raised, if they are wedged between two high tones. L raising is argued to be a local carryover effect (co-articulation). Further, it is demonstrated that global anticipatory raising takes place. It is shown that Akan speakers anticipate the length of an IP. Preplanning (anticipatory raising) is argued to be an important process at the level of pitch implementation. It serves to ensure that declination can be maintained throughout the IP, which prevents pitch resetting.
The melody of an Akan sentence is largely determined by the choice of words. The inventory of post-lexical tones is small. It consists of post-lexical register tones, which trigger declination and post-lexical intonational tones, which signal sentence type. The overall melodic shape is falling. At the local level, H raising and L raising occur. At the global level, initial low and high tones are realized higher if they occur in a long and/or complex sentence. This dissertation shows that many factors, which emerge at different levels of the tone production process, contribute to the surface form of tones in Akan.