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In many biological and environmental applications spatially resolved sensing of molecular oxygen is desirable. A powerful tool for distributed measurements is optical time domain reflectometry (OTDR) which is often used in the field of telecommunications. We combine this technique with a novel optical oxygen sensor dye, triangular-[4] phenylene (TP), immobilized in a polymer matrix. The TP luminescence decay time is 86 ns. The short decay time of the sensor dye is suitable to achieve a spatial resolution of some meters. In this paper we present the development and characterization of a reflectometer in the UV range of the electromagnetic spectrum as well as optical oxygen sensing with different fiber arrangements.
When playing violent video games, aggressive actions are performed against the background of an originally neutral environment, and associations are formed between cues related to violence and contextual features. This experiment examined the hypothesis that neutral contextual features of a virtual environment become associated with aggressive meaning and acquire the function of primes for aggressive cognitions. Seventy-six participants were assigned to one of two violent video game conditions that varied in context (ship vs. city environment) or a control condition. Afterwards, they completed a Lexical Decision Task to measure the accessibility of aggressive cognitions in which they were primed either with ship-related or city-related words. As predicted, participants who had played the violent game in the ship environment had shorter reaction times for aggressive words following the ship primes than the city primes, whereas participants in the city condition responded faster to the aggressive words following the city primes compared to the ship primes. No parallel effect was observed for the non-aggressive targets. The findings indicate that the associations between violent and neutral cognitions learned during violent game play facilitate the accessibility of aggressive cognitions.
Various 1,6- and 1,8-naphthalenophanes were synthesized by using the Photo-Dehydro-Diels-Alder (PDDA) reaction of bis-ynones. These compounds are easily accessible from omega-(3-iodophenyl)carboxylic acids in three steps. The obtained naphthalenophanes are axially chiral and the activation barrier for the atropisomerization could be determined in some cases by means of dynamic NMR (DNMR) and/or dynamic HPLC (DHPLC) experiments.
Background: DNA fragments carrying internal recognition sites for the restriction endonucleases intended for cloning into a target plasmid pose a challenge for conventional cloning.
Results: A method for directional insertion of DNA fragments into plasmid vectors has been developed. The target sequence is amplified from a template DNA sample by PCR using two oligonucleotides each containing a single deoxyinosine base at the third position from the 5' end. Treatment of such PCR products with endonuclease V generates 3' protruding ends suitable for ligation with vector fragments created by conventional restriction endonuclease reactions.
Conclusions: The developed approach generates terminal cohesive ends without the use of Type II restriction endonucleases, and is thus independent from the DNA sequence. Due to PCR amplification, minimal amounts of template DNA are required. Using the robust Taq enzyme or a proofreading Pfu DNA polymerase mutant, the method is applicable to a broad range of insert sequences. Appropriate primer design enables direct incorporation of terminal DNA sequence modifications such as tag addition, insertions, deletions and mutations into the cloning strategy. Further, the restriction sites of the target plasmid can be either retained or removed.
The dynamics of external contributions to the geomagnetic field is investigated by applying time-frequency methods to magnetic observatory data. Fractal models and multiscale analysis enable obtaining maximum quantitative information related to the short-term dynamics of the geomagnetic field activity. The stochastic properties of the horizontal component of the transient external field are determined by searching for scaling laws in the power spectra. The spectrum fits a power law with a scaling exponent β, a typical characteristic of self-affine time-series. Local variations in the power-law exponent are investigated by applying wavelet analysis to the same time-series. These analyses highlight the self-affine properties of geomagnetic perturbations and their persistence. Moreover, they show that the main phases of sudden storm disturbances are uniquely characterized by a scaling exponent varying between 1 and 3, possibly related to the energy contained in the external field. These new findings suggest the existence of a long-range dependence, the scaling exponent being an efficient indicator of geomagnetic activity and singularity detection. These results show that by using magnetogram regularity to reflect the magnetosphere activity, a theoretical analysis of the external geomagnetic field based on local power-law exponents is possible.
In this paper, we determine necessary and sufficient conditions for Bruck-Reilly and generalized Bruck-Reilly ∗-extensions of arbitrary monoids to be regular, coregular and strongly π-inverse. These semigroup classes have applications in various field of mathematics, such as matrix theory, discrete mathematics and p-adic analysis (especially in operator theory). In addition, while regularity and coregularity have so many applications in the meaning of boundaries (again in operator theory), inverse monoids and Bruck-Reilly extensions contain a mixture fixed-point results of algebra, topology and geometry within the purposes of this journal.
The genetic code is degenerate; thus, protein evolution does not uniquely determine the coding sequence. One of the puzzles in evolutionary genetics is therefore to uncover evolutionary driving forces that result in specific codon choice. In many bacteria, the first 5-10 codons of protein-coding genes are often codons that are less frequently used in the rest of the genome, an effect that has been argued to arise from selection for slowed early elongation to reduce ribosome traffic jams. However, genome analysis across many species has demonstrated that the region shows reduced mRNA folding consistent with pressure for efficient translation initiation. This raises the possibility that unusual codon usage is a side effect of selection for reduced mRNA structure. Here we discriminate between these two competing hypotheses, and show that in bacteria selection favours codons that reduce mRNA folding around the translation start, regardless of whether these codons are frequent or rare. Experiments confirm that primarily mRNA structure, and not codon usage, at the beginning of genes determines the translation rate.
TRAPID
(2013)
Transcriptome analysis through next-generation sequencing technologies allows the generation of detailed gene catalogs for non-model species, at the cost of new challenges with regards to computational requirements and bioinformatics expertise. Here, we present TRAPID, an online tool for the fast and efficient processing of assembled RNA-Seq transcriptome data, developed to mitigate these challenges. TRAPID offers high-throughput open reading frame detection, frameshift correction and includes a functional, comparative and phylogenetic toolbox, making use of 175 reference proteomes. Benchmarking and comparison against state-of-the-art transcript analysis tools reveals the efficiency and unique features of the TRAPID system. TRAPID is freely available at http://bioinformatics.psb.ugent.be/webtools/trapid/.
Growing out of the crisis
(2013)
Greece’s currently planned institutional reforms will help to get the country going with limited economic growth. With an economy based primarily on tourism, trade, and agriculture, Greece lacks an established competitive industry and an innovation-friendly environment, resulting in a low export ratio given the small size of the country and its long-time EU-membership. Instead, Greece exports only its nation's talent, with low returns. To become prosperous, the country must better capitalize on its Eurozone membership and add innovative sectors to its economic structure. Given Greece's hidden assets, such as the attractiveness of the country, a small number of strong research centers and an impressive diaspora in research, finance and business, we envision a Greek “Silicon Valley” and propose a ten point policy plan to achieve that goal.
Background: The linear noise approximation (LNA) is commonly used to predict how noise is regulated and exploited at the cellular level. These predictions are exact for reaction networks composed exclusively of first order reactions or for networks involving bimolecular reactions and large numbers of molecules. It is however well known that gene regulation involves bimolecular interactions with molecule numbers as small as a single copy of a particular gene. It is therefore questionable how reliable are the LNA predictions for these systems.
Results: We implement in the software package intrinsic Noise Analyzer (iNA), a system size expansion based method which calculates the mean concentrations and the variances of the fluctuations to an order of accuracy higher than the LNA. We then use iNA to explore the parametric dependence of the Fano factors and of the coefficients of variation of the mRNA and protein fluctuations in models of genetic networks involving nonlinear protein degradation, post-transcriptional, post-translational and negative feedback regulation. We find that the LNA can significantly underestimate the amplitude and period of noise-induced oscillations in genetic oscillators. We also identify cases where the LNA predicts that noise levels can be optimized by tuning a bimolecular rate constant whereas our method shows that no such regulation is possible. All our results are confirmed by stochastic simulations.
Conclusion: The software iNA allows the investigation of parameter regimes where the LNA fares well and where it does not. We have shown that the parametric dependence of the coefficients of variation and Fano factors for common gene regulatory networks is better described by including terms of higher order than LNA in the system size expansion. This analysis is considerably faster than stochastic simulations due to the extensive ensemble averaging needed to obtain statistically meaningful results. Hence iNA is well suited for performing computationally efficient and quantitative studies of intrinsic noise in gene regulatory networks.
Research indicates that evidence-based policy making is most successful when public administrators refer to diversified information portfolios. With the rising prominence of social media in the last decade, this paper argues that governments can benefit from integrating this publically available, user-generated data through the technique of social media analytics (SMA). There are already several initiatives set up to predict future policy issues, e.g. for the policy fields of crisis mitigation or migrant integration insights. The authors analyse these endeavours and their potential for providing more efficient and effective public policies. Furthermore, they scrutinise the challenges to governmental SMA usage in particular with regards to legal and ethical aspects. Reflecting the latter, this paper provides forward-looking recommendations on how these technologies can best be used for future policy making in a legally and ethically sound manner.
Background: With increasing age neuromuscular deficits (e.g., sarcopenia) may result in impaired physical performance and an increased risk for falls. Prominent intrinsic fall-risk factors are age-related decreases in balance and strength / power performance as well as cognitive decline. Additional studies are needed to develop specifically tailored exercise programs for older adults that can easily be implemented into clinical practice. Thus, the objective of the present trial is to assess the effects of a fall prevention program that was developed by an interdisciplinary expert panel on measures of balance, strength / power, body composition, cognition, psychosocial well-being, and falls self-efficacy in healthy older adults. Additionally, the time-related effects of detraining are tested.
Methods/Design: Healthy old people (n = 54) between the age of 65 to 80 years will participate in this trial. The testing protocol comprises tests for the assessment of static / dynamic steady-state balance (i.e., Sharpened Romberg Test, instrumented gait analysis), proactive balance (i.e., Functional Reach Test; Timed Up and Go Test), reactive balance (i.e., perturbation test during bipedal stance; Push and Release Test), strength (i.e., hand grip strength test; Chair Stand Test), and power (i.e., Stair Climb Power Test; countermovement jump). Further, body composition will be analysed using a bioelectrical impedance analysis system. In addition, questionnaires for the assessment of psychosocial (i.e., World Health Organisation Quality of Life Assessment-Bref), cognitive (i.e., Mini Mental State Examination), and fall risk determinants (i.e., Fall Efficacy Scale -International) will be included in the study protocol. Participants will be randomized into two intervention groups or the control / waiting group. After baseline measures, participants in the intervention groups will conduct a 12-week balance and strength / power exercise intervention 3 times per week, with each training session lasting 30 min. (actual training time). One intervention group will complete an extensive supervised training program, while the other intervention group will complete a short version (` 3 times 3') that is home-based and controlled by weekly phone calls. Post-tests will be conducted right after the intervention period. Additionally, detraining effects will be measured 12 weeks after program cessation. The control group / waiting group will not participate in any specific intervention during the experimental period, but will receive the extensive supervised program after the experimental period.
Discussion: It is expected that particularly the supervised combination of balance and strength / power training will improve performance in variables of balance, strength / power, body composition, cognitive function, psychosocial well-being, and falls self-efficacy of older adults. In addition, information regarding fall risk assessment, dose-response-relations, detraining effects, and supervision of training will be provided. Further, training-induced health-relevant changes, such as improved performance in activities of daily living, cognitive function, and quality of life, as well as a reduced risk for falls may help to lower costs in the health care system. Finally, practitioners, therapists, and instructors will be provided with a scientifically evaluated feasible, safe, and easy-to-administer exercise program for fall prevention.
Portal Wissen = Borders
(2013)
The new edition of the Potsdam Research Magazine “Portal Wissen” approaches the subject “Borders” from different perspectives.
As a linguist, this headline makes me think of linguistic borders and the effects that might result from the contact of two languages at a particular border. There is, for instance, ample evidence of code-switching, i.e. the use of material from at least two languages in a single utterance. The reasons for code-switching can be manifold. On the one hand, code-switching may result from a limited language competence, for example if a speaker lacks a particular word in a nonnative language. On the other hand, code-switching may be a matter of prestige if the speaker wants to demonstrate his or her affiliation to a certain social group by switching languages. If code-switching does not only occur sporadically but involves whole language communities over a longer period of time, it can result in significant changes of the involved languages. Which language “gives” and which one “takes” is determined by sociolinguistic factors. It is, hence, quite easy to predict that German varieties spoken in language islands in South and Eastern Europe as well as in North and Latin America will absorb more and more language material from their neighbouring languages until they disappear unless political will strives to preserve these language varieties. Increasing mobility of modern societies has multiplied the extent and the intensity of language contact and certainly comprises a large number of different contact situations besides the one most commonly known, i.e. the contact between German and English.
From a historic point of view, German witnesses a strong influence of various Romance languages such as Latin, French and Italian. In Potsdam, one cannot help being reminded of the French influence during the 18th century.
Overcoming language borders becomes also apparent in the everyday life of an international research university. In March this year, the Annual Conference of the German Linguistic Society took place in Potsdam, with more than 500 participants. Lingua franca of this conference was English. Compared to previous conferences, this further increased the number of international participants.
The articles in this edition illustrate various approaches to the topic “Borders”: On the trail of “Boundary Surveys”, we follow the Australian explorer Ludwig Leichhardt. “Travellers Across Borders” is focussed on articles dealing with the literature of the colonial Caribbean or with the work of an Italian geologist deep beneath the earth’s surface, for example. Looking for the “Boundless”, our authors follow scientists who discuss questions like “Why love hurts?”. The present issue of “Portal Wissen” also takes into account “Drawing Up Borders” in an article that is concerned with the limits of workrelated stress. Instances of successful “Border Crossing” are provided by the “Handkerchief Lab” as well as by new biotechnological applications.
I would like to wish you inspiring border experiences, hoping that you will get many impulses for crossing professional borders in your field of expertise.
Prof. Ulrike Demske
Professor of the History and the Varieties of the German Language
Vice President International Affairs, Alumni and Fundraising
Portal Wissen = Layers
(2013)
The latest edition of our Potsdam Research Magazine “Portal Wissen” addresses the topic “Layers” in many different ways. Geoscientists often deal with layers: layers of soil, sediment, or rock are the evidence of repeated and long-lasting processes of erosion and sedimentation that took place in the early history of the earth. For instance, mountains are eroded by water, ice and wind. The sand that results from that erosion might eventually form a new layer on the ocean floor known as a sediment horizon. After tens of millions of years, tectonic plate movements can deform the ocean floor, pushing it upwards as mountains are created, bringing the layers of sand from former mountain chains together with fossilized sea dwellers into the realm of climbers and mountaineers – a fundamental cycle within the Earth system that was succinctly described by Ibn Sina nearly 1000 years ago, and later by Charles Darwin when he was crossing the Andes.
The landscape around us overlays the products of recent processes with those from the past. Slow processes or extreme events that happen very rarely – like floods, earthquakes or rockslides – wipe out certain characteristics, while others remain on the surface. In this sense, the landscape is like a palimpsest – a piece of parchment that monks in the Middle Ages scraped clean again and again to write something new. Analysing rock layers and soil is similar to the work of a detective. Geophysical deep sounding with sound and radar waves, precise measurements of motions related to earthquakes, and deep boreholes each provide a glimpse of the characteristics of what lies beneath us, giving us a better understanding of spatial distribution of the various layers. Fossils can tell us the age of a layer of sediment, while radiometric isotopes in minerals reveal how quickly a rock moved from deep within the Earth up to the surface, perhaps during the process of mountain building. Thin layers of ash tell us when there was a devastating volcanic eruption that influenced environmental conditions. The shape, gradation, and surface conditions of sand grains reflect whether wind or water was responsible for their transport. We know, for instance, that northern Germany was a desert landscape more than 260 million years ago. At that time, the wind made huge dunes migrate across the region. Over time, climate and vegetation slowly alter the physical and chemical characteristics of sand and rock at the surface, turning them into soil, the epidermis of our planet. Mineralogical analyses of layers of the soil layer tell us whether the climate was dry or wet. These kinds of observations allow us to reconstruct links between our climate system and processes that have taken place on the Earth’s surface, as well as those processes that originate at much deeper levels. The clues we use might be hidden under the surface of the earth or clearly visible on the surface, like in the mountains, or even in freshly cut rock alongside roads.
On the following pages, we invite you to accompany scientists from Potsdam into their world of research. They track hidden traces of longgone earthquakes in the Tien Shan Mountains; they discover ancient forms of life in deep-sea sediments. They even examine layers in outer space that can tell us something about the formation of planets. “Portal Wissen” not only presents scientists of the University of Potsdam who deal with the sequence of layers formed by solid rock, but also those scientists who deal with levels of education or social strata. Research scientists explain how to implement the social mission of inclusion in teaching, and how pupils from the Berlin district Kreuzberg examine language in urban neighbourhoods together with students from the University of Potsdam.
Although these types of “layers” are very different, they all have something in common. Their structure and profile are evidence of continuously changing conditions. The present will leave traces and layers that future geoscientists will measure and examine. We already speak of the Anthropocene, a geological era dominated by humans, which is characterized by far-reaching changes in erosion and sedimentation rates, and the displacement of natural habitats. I hope that you will discover exciting and inspiring stories in this edition. And remember – it is always worth having a look beneath the surface.
Prof. Manfred Strecker, PHD
Professor of Geology
Background: Recent studies have demonstrated a superior diagnostic accuracy of cardiovascular magnetic resonance (CMR) for the detection of coronary artery disease (CAD). We aimed to determine the comparative cost-effectiveness of CMR versus single-photon emission computed tomography (SPECT).
Methods: Based on Bayes' theorem, a mathematical model was developed to compare the cost-effectiveness and utility of CMR with SPECT in patients with suspected CAD. Invasive coronary angiography served as the standard of reference. Effectiveness was defined as the accurate detection of CAD, and utility as the number of quality-adjusted life-years (QALYs) gained. Model input parameters were derived from the literature, and the cost analysis was conducted from a German health care payer's perspective. Extensive sensitivity analyses were performed.
Results: Reimbursement fees represented only a minor fraction of the total costs incurred by a diagnostic strategy. Increases in the prevalence of CAD were generally associated with improved cost-effectiveness and decreased costs per utility unit (Delta QALY). By comparison, CMR was consistently more cost-effective than SPECT, and showed lower costs per QALY gained. Given a CAD prevalence of 0.50, CMR was associated with total costs of (sic)6,120 for one patient correctly diagnosed as having CAD and with (sic)2,246 per Delta QALY gained versus (sic)7,065 and (sic)2,931 for SPECT, respectively. Above a threshold value of CAD prevalence of 0.60, proceeding directly to invasive angiography was the most cost-effective approach.
Conclusions: In patients with low to intermediate CAD probabilities, CMR is more cost-effective than SPECT. Moreover, lower costs per utility unit indicate a superior clinical utility of CMR.
We study origin, parameter optimization, and thermodynamic efficiency of isothermal rocking ratchets based on fractional subdiffusion within a generalized non-Markovian Langevin equation approach. A corresponding multi-dimensional Markovian embedding dynamics is realized using a set of auxiliary Brownian particles elastically coupled to the central Brownian particle (see video on the journal web site). We show that anomalous subdiffusive transport emerges due to an interplay of nonlinear response and viscoelastic effects for fractional Brownian motion in periodic potentials with broken space-inversion symmetry and driven by a time-periodic field. The anomalous transport becomes optimal for a subthreshold driving when the driving period matches a characteristic time scale of interwell transitions. It can also be optimized by varying temperature, amplitude of periodic potential and driving strength. The useful work done against a load shows a parabolic dependence on the load strength. It grows sublinearly with time and the corresponding thermodynamic efficiency decays algebraically in time because the energy supplied by the driving field scales with time linearly. However, it compares well with the efficiency of normal diffusion rocking ratchets on an appreciably long time scale.
During an unusually massive filament eruption on 7 June 2011, SDO/AIA imaged for the first time significant EUV emission around a magnetic reconnection region in the solar corona. The reconnection occurred between magnetic fields of the laterally expanding CME and a neighbouring active region. A pre-existing quasi-separatrix layer was activated in the process. This scenario is supported by data-constrained numerical simulations of the eruption. Observations show that dense cool filament plasma was re-directed and heated in situ, producing coronal-temperature emission around the reconnection region. These results provide the first direct observational evidence, supported by MHD simulations and magnetic modelling, that a large-scale re-configuration of the coronal magnetic field takes place during solar eruptions via the process of magnetic reconnection.
Understanding the magnetic configuration of the source regions of coronal mass ejections (CMEs) is vital in order to determine the trigger and driver of these events. Observations of four CME productive active regions are presented here, which indicate that the pre-eruption magnetic configuration is that of a magnetic flux rope. The flux ropes are formed in the solar atmosphere by the process known as flux cancellation and are stable for several hours before the eruption. The observations also indicate that the magnetic structure that erupts is not the entire flux rope as initially formed, raising the question of whether the flux rope is able to undergo a partial eruption or whether it undergoes a transition in specific flux rope configuration shortly
before the CME.
In Germany, active bat rabies surveillance was conducted between 1993 and 2012. A total of 4546 oropharyngeal swab samples from 18 bat species were screened for the presence of EBLV-1- , EBLV-2- and BBLV-specific RNA. Overall, 0 center dot 15% of oropharyngeal swab samples tested EBLV-1 positive, with the majority originating from Eptesicus serotinus. Interestingly, out of seven RT-PCR-positive oropharyngeal swabs subjected to virus isolation, viable virus was isolated from a single serotine bat (E. serotinus). Additionally, about 1226 blood samples were tested serologically, and varying virus neutralizing antibody titres were found in at least eight different bat species. The detection of viral RNA and seroconversion in repeatedly sampled serotine bats indicates long-term circulation of the virus in a particular bat colony. The limitations of random-based active bat rabies surveillance over passive bat rabies surveillance and its possible application of targeted approaches for future research activities on bat lyssavirus dynamics and maintenance are discussed.
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.
User-centered design processes are the first choice when new interactive systems or services are developed to address real customer needs and provide a good user experience. Common tools for collecting user research data, conducting brainstormings, or sketching ideas are whiteboards and sticky notes. They are ubiquitously available, and no technical or domain knowledge is necessary to use them. However, traditional pen and paper tools fall short when saving the content and sharing it with others unable to be in the same location. They are also missing further digital advantages such as searching or sorting content. Although research on digital whiteboard and sticky note applications has been conducted for over 20 years, these tools are not widely adopted in company contexts. While many research prototypes exist, they have not been used for an extended period of time in a real-world context. The goal of this thesis is to investigate what the enablers and obstacles for the adoption of digital whiteboard systems are. As an instrument for different studies, we developed the Tele-Board software system for collaborative creative work. Based on interviews, observations, and findings from former research, we tried to transfer the analog way of working to the digital world. Being a software system, Tele-Board can be used with a variety of hardware and does not depend on special devices. This feature became one of the main factors for adoption on a larger scale. In this thesis, I will present three studies on the use of Tele-Board with different user groups and foci. I will use a combination of research methods (laboratory case studies and data from field research) with the overall goal of finding out when a digital whiteboard system is used and in which cases not. Not surprisingly, the system is used and accepted if a user sees a main benefit that neither analog tools nor other applications can offer. However, I found that these perceived benefits are very different for each user and usage context. If a tool provides possibilities to use in different ways and with different equipment, the chances of its adoption by a larger group increase. Tele-Board has now been in use for over 1.5 years in a global IT company in at least five countries with a constantly growing user base. Its use, advantages, and disadvantages will be described based on 42 interviews and usage statistics from server logs. Through these insights and findings from laboratory case studies, I will present a detailed analysis of digital whiteboard use in different contexts with design implications for future systems.
HPI Future SOC Lab
(2013)
The “HPI Future SOC Lab” is a cooperation of the Hasso-Plattner-Institut (HPI) and industrial partners. Its mission is to enable and promote exchange and interaction between the research community and the industrial partners. The HPI Future SOC Lab provides researchers with free of charge access to a complete infrastructure of state of the art hard- and software. This infrastructure includes components, which might be too expensive for an ordinary research environment, such as servers with up to 64 cores. The offerings address researchers particularly from but not limited to the areas of computer science and business information systems. Main areas of research include cloud computing, parallelization, and In-Memory technologies. This technical report presents results of research projects executed in 2012. Selected projects have presented their results on June 18th and November 26th 2012 at the Future SOC Lab Day events.
This document presents a formula selection system for classical first order theorem proving based on the relevance of formulae for the proof of a conjecture. It is based on unifiability of predicates and is also able to use a linguistic approach for the selection. The scope of the technique is the reduction of the set of formulae and the increase of the amount of provable conjectures in a given time. Since the technique generates a subset of the formula set, it can be used as a preprocessor for automated theorem proving. The document contains the conception, implementation and evaluation of both selection concepts. While the one concept generates a search graph over the negation normal forms or Skolem normal forms of the given formulae, the linguistic concept analyses the formulae and determines frequencies of lexemes and uses a tf-idf weighting algorithm to determine the relevance of the formulae. Though the concept is built for first order logic, it is not limited to it. The concept can be used for higher order and modal logik, too, with minimal adoptions. The system was also evaluated at the world championship of automated theorem provers (CADE ATP Systems Competition, CASC-24) in combination with the leanCoP theorem prover and the evaluation of the results of the CASC and the benchmarks with the problems of the CASC of the year 2012 (CASC-J6) show that the concept of the system has positive impact to the performance of automated theorem provers. Also, the benchmarks with two different theorem provers which use different calculi have shown that the selection is independent from the calculus. Moreover, the concept of TEMPLAR has shown to be competitive to some extent with the concept of SinE and even helped one of the theorem provers to solve problems that were not (or slower) solved with SinE selection in the CASC. Finally, the evaluation implies that the combination of the unification based and linguistic selection yields more improved results though no optimisation was done for the problems.
Pronoun resolution normally takes place without conscious effort or awareness, yet the processes behind it are far from straightforward. A large number of cues and constraints have previously been recognised as playing a role in the identification and integration of potential antecedents, yet there is considerable debate over how these operate within the resolution process. The aim of this thesis is to investigate how the parser handles multiple antecedents in order to understand more about how certain information sources play a role during pronoun resolution. I consider how both structural information and information provided by the prior discourse is used during online processing. This is investigated through several eye tracking during reading experiments that are complemented by a number of offline questionnaire experiments. I begin by considering how condition B of the Binding Theory (Chomsky 1981; 1986) has been captured in pronoun processing models; some researchers have claimed that processing is faithful to syntactic constraints from the beginning of the search (e.g. Nicol and Swinney 1989), while others have claimed that potential antecedents which are ruled out on structural grounds nonetheless affect processing, because the parser must also pay attention to a potential antecedent’s features (e.g. Badecker and Straub 2002). My experimental findings demonstrate that the parser is sensitive to the subtle changes in syntactic configuration which either allow or disallow pronoun reference to a local antecedent, and indicate that the parser is normally faithful to condition B at all stages of processing. Secondly, I test the Primitives of Binding hypothesis proposed by Koornneef (2008) based on work by Reuland (2001), which is a modular approach to pronoun resolution in which variable binding (a semantic relationship between pronoun and antecedent) takes place before coreference. I demonstrate that a variable-binding (VB) antecedent is not systematically considered earlier than a coreference (CR) antecedent online. I then go on to explore whether these findings could be attributed to the linear order of the antecedents, and uncover a robust recency preference both online and offline. I consider what role the factor of recency plays in pronoun resolution and how it can be reconciled with the first-mention advantage (Gernsbacher and Hargreaves 1988; Arnold 2001; Arnold et al., 2007). Finally, I investigate how aspects of the prior discourse affect pronoun resolution. Prior discourse status clearly had an effect on pronoun resolution, but an antecedent’s appearance in the previous context was not always facilitative; I propose that this is due to the number of topic switches that a reader must make, leading to a lack of discourse coherence which has a detrimental effect on pronoun resolution. The sensitivity of the parser to structural cues does not entail that cue types can be easily separated into distinct sequential stages, and I therefore propose that the parser is structurally sensitive but not modular. Aspects of pronoun resolution can be captured within a parallel constraints model of pronoun resolution, however, such a model should be sensitive to the activation of potential antecedents based on discourse factors, and structural cues should be strongly weighted.
Galaxy clusters are the largest known gravitationally bound objects, their study is important for both an intrinsic understanding of their systems and an investigation of the large scale structure of the universe. The multi- component nature of galaxy clusters offers multiple observable signals across the electromagnetic spectrum. At X-ray wavelengths, galaxy clusters are simply identified as X-ray luminous, spatially extended, and extragalactic sources. X-ray observations offer the most powerful technique for constructing cluster catalogues. The main advantages of the X-ray cluster surveys are their excellent purity and completeness and the X-ray observables are tightly correlated with mass, which is indeed the most fundamental parameter of clusters. In my thesis I have conducted the 2XMMi/SDSS galaxy cluster survey, which is a serendipitous search for galaxy clusters based on the X-ray extended sources in the XMM-Newton Serendipitous Source Catalogue (2XMMi-DR3). The main aims of the survey are to identify new X-ray galaxy clusters, investigate their X-ray scaling relations, identify distant cluster candidates, and study the correlation of the X-ray and optical properties. The survey is constrained to those extended sources that are in the footprint of the Sloan Digital Sky Survey (SDSS) in order to be able to identify the optical counterparts as well as to measure their redshifts that are mandatory to measure their physical properties. The overlap area be- tween the XMM-Newton fields and the SDSS-DR7 imaging, the latest SDSS data release at the starting of the survey, is 210 deg^2. The survey comprises 1180 X-ray cluster candidates with at least 80 background-subtracted photon counts, which passed the quality control process. To measure the optical redshifts of the X-ray cluster candidates, I used three procedures; (i) cross-matching these candidates with the recent and largest optically selected cluster catalogues in the literature, which yielded the photometric redshifts of about a quarter of the X-ray cluster candidates. (ii) I developed a finding algorithm to search for overdensities of galaxies at the positions of the X-ray cluster candidates in the photometric redshift space and to measure their redshifts from the SDSS-DR8 data, which provided the photometric redshifts of 530 groups/clusters. (iii) I developed an algorithm to identify the cluster candidates associated with spectroscopically targeted Luminous Red Galaxies (LRGs) in the SDSS-DR9 and to measure the cluster spectroscopic redshift, which provided 324 groups and clusters with spectroscopic confirmation based on spectroscopic redshift of at least one LRG. In total, the optically confirmed cluster sample comprises 574 groups and clusters with redshifts (0.03 ≤ z ≤ 0.77), which is the largest X-ray selected cluster catalogue to date based on observations from the current X-ray observatories (XMM-Newton, Chandra, Suzaku, and Swift/XRT). Among the cluster sample, about 75 percent are newly X-ray discovered groups/clusters and 40 percent are new systems to the literature. To determine the X-ray properties of the optically confirmed cluster sample, I reduced and analysed their X-ray data in an automated way following the standard pipelines of processing the XMM-Newton data. In this analysis, I extracted the cluster spectra from EPIC(PN, MOS1, MOS2) images within an optimal aperture chosen to maximise the signal-to-noise ratio. The spectral fitting procedure provided the X-ray temperatures kT (0.5 - 7.5 keV) for 345 systems that have good quality X-ray data. For all the optically confirmed cluster sample, I measured the physical properties L500 (0.5 x 10^42 – 1.2 x 10^45 erg s-1 ) and M500 (1.1 x 10^13 – 4.9 x 10^14 M⊙) from an iterative procedure using published scaling relations. The present X-ray detected groups and clusters are in the low and intermediate luminosity regimes apart from few luminous systems, thanks to the XMM-Newton sensitivity and the available XMM-Newton deep fields The optically confirmed cluster sample with measurements of redshift and X-ray properties can be used for various astrophysical applications. As a first application, I investigated the LX - T relation for the first time based on a large cluster sample of 345 systems with X-ray spectroscopic parameters drawn from a single survey. The current sample includes groups and clusters with wide ranges of redshifts, temperatures, and luminosities. The slope of the relation is consistent with the published ones of nearby clusters with higher temperatures and luminosities. The derived relation is still much steeper than that predicted by self-similar evolution. I also investigated the evolution of the slope and the scatter of the LX - T relation with the cluster redshift. After excluding the low luminosity groups, I found no significant changes of the slope and the intrinsic scatter of the relation with redshift when dividing the sample into three redshift bins. When including the low luminosity groups in the low redshift subsample, I found its LX - T relation becomes after than the relation of the intermediate and high redshift subsamples. As a second application of the optically confirmed cluster sample from our ongoing survey, I investigated the correlation between the cluster X-ray and the optical parameters that have been determined in a homogenous way. Firstly, I investigated the correlations between the BCG properties (absolute magnitude and optical luminosity) and the cluster global proper- ties (redshift and mass). Secondly, I computed the richness and the optical luminosity within R500 of a nearby subsample (z ≤ 0.42, with a complete membership detection from the SDSS data) with measured X-ray temperatures from our survey. The relation between the estimated optical luminosity and richness is also presented. Finally, the correlation between the cluster optical properties (richness and luminosity) and the cluster global properties (X-ray luminosity, temperature, mass) are investigated.
LCST-type synthetic thermoresponsive polymers can reversibly respond to certain stimuli in aqueous media with a massive change of their physical state. When fluorophores, that are sensitive to such changes, are incorporated into the polymeric structure, the response can be translated into a fluorescence signal. Based on this idea, this thesis presents sensing schemes which transduce the stimuli-induced variations in the solubility of polymer chains with covalently-bound fluorophores into a well-detectable fluorescence output. Benefiting from the principles of different photophysical phenomena, i.e. of fluorescence resonance energy transfer and solvatochromism, such fluorescent copolymers enabled monitoring of stimuli such as the solution temperature and ionic strength, but also of association/disassociation mechanisms with other macromolecules or of biochemical binding events through remarkable changes in their fluorescence properties. For instance, an aqueous ratiometric dual sensor for temperature and salts was developed, relying on the delicate supramolecular assembly of a thermoresponsive copolymer with a thiophene-based conjugated polyelectrolyte. Alternatively, by taking advantage of the sensitivity of solvatochromic fluorophores, an increase in solution temperature or the presence of analytes was signaled as an enhancement of the fluorescence intensity. A simultaneous use of the sensitivity of chains towards the temperature and a specific antibody allowed monitoring of more complex phenomena such as competitive binding of analytes. The use of different thermoresponsive polymers, namely poly(N-isopropylacrylamide) and poly(meth)acrylates bearing oligo(ethylene glycol) side chains, revealed that the responsive polymers differed widely in their ability to perform a particular sensing function. In order to address questions regarding the impact of the chemical structure of the host polymer on the sensing performance, the macromolecular assembly behavior below and above the phase transition temperature was evaluated by a combination of fluorescence and light scattering methods. It was found that although the temperature-triggered changes in the macroscopic absorption characteristics were similar for these polymers, properties such as the degree of hydration or the extent of interchain aggregations differed substantially. Therefore, in addition to the demonstration of strategies for fluorescence-based sensing with thermoresponsive polymers, this work highlights the role of the chemical structure of the two popular thermoresponsive polymers on the fluorescence response. The results are fundamentally important for the rational choice of polymeric materials for a specific sensing strategy.
This thesis gives formal definitions of discourse-givenness, coreference and reference, and reports on experiments with computational models of discourse-givenness of noun phrases for English and German. Definitions are based on Bach's (1987) work on reference, Kibble and van Deemter's (2000) work on coreference, and Kamp and Reyle's Discourse Representation Theory (1993). For the experiments, the following corpora with coreference annotation were used: MUC-7, OntoNotes and ARRAU for Englisch, and TueBa-D/Z for German. As for classification algorithms, they cover J48 decision trees, the rule based learner Ripper, and linear support vector machines. New features are suggested, representing the noun phrase's specificity as well as its context, which lead to a significant improvement of classification quality.
Several mechanisms are proposed to be part of the earthquake triggering process, including static stress interactions and dynamic stress transfer. Significant differences of these mechanisms are particularly expected in the spatial distribution of aftershocks. However, testing the different hypotheses is challenging because it requires the consideration of the large uncertainties involved in stress calculations as well as the appropriate consideration of secondary aftershock triggering which is related to stress changes induced by smaller pre- and aftershocks. In order to evaluate the forecast capability of different mechanisms, I take the effect of smaller--magnitude earthquakes into account by using the epidemic type aftershock sequence (ETAS) model where the spatial probability distribution of direct aftershocks, if available, is correlated to alternative source information and mechanisms. Surface shaking, rupture geometry, and slip distributions are tested. As an approximation of the shaking level, ShakeMaps are used which are available in near real-time after a mainshock and thus could be used for first-order forecasts of the spatial aftershock distribution. Alternatively, the use of empirical decay laws related to minimum fault distance is tested and Coulomb stress change calculations based on published and random slip models. For comparison, the likelihood values of the different model combinations are analyzed in the case of several well-known aftershock sequences (1992 Landers, 1999 Hector Mine, 2004 Parkfield). The tests show that the fault geometry is the most valuable information for improving aftershock forecasts. Furthermore, they reveal that static stress maps can additionally improve the forecasts of off--fault aftershock locations, while the integration of ground shaking data could not upgrade the results significantly. In the second part of this work, I focused on a procedure to test the information content of inverted slip models. This allows to quantify the information gain if this kind of data is included in aftershock forecasts. For this purpose, the ETAS model based on static stress changes, which is introduced in part one, is applied. The forecast ability of the models is systematically tested for several earthquake sequences and compared to models using random slip distributions. The influence of subfault resolution and segment strike and dip is tested. Some of the tested slip models perform very good, in that cases almost no random slip models are found to perform better. Contrastingly, for some of the published slip models, almost all random slip models perform better than the published slip model. Choosing a different subfault resolution hardly influences the result, as long the general slip pattern is still reproducible. Whereas different strike and dip values strongly influence the results depending on the standard deviation chosen, which is applied in the process of randomly selecting the strike and dip values.
Information flows in EU policy-making are heavily dependent on personal networks, both within the Brussels sphere but also reaching outside the narrow limits of the Belgian capital. These networks develop for example in the course of formal and informal meetings or at the sidelines of such meetings. A plethora of committees at European, transnational and regional level provides the basis for the establishment of pan-European networks. By studying affiliation to those committees, basic network structures can be uncovered. These affiliation network structures can then be used to predict EU information flows, assuming that certain positions within the network are advantageous for tapping into streams of information while others are too remote and peripheral to provide access to information early enough. This study has tested those assumptions for the case of the reform of the Common Fisheries Policy for the time after 2012. Through the analysis of an affiliation network based on participation in 10 different fisheries policy committees over two years (2009 and 2010), network data for an EU-wide network of about 1300 fisheries interest group representatives and more than 200 events was collected. The structure of this network showed a number of interesting patterns, such as – not surprisingly – a rather central role of Brussels-based committees but also close relations of very specific interests to the Brussels-cluster and stronger relations between geographically closer maritime regions. The analysis of information flows then focused on access to draft EU Commission documents containing the upcoming proposal for a new basic regulation of the Common Fisheries Policy. It was first documented that it would have been impossible to officially obtain this document and that personal networks were thus the most likely sources for fisheries policy actors to obtain access to these “leaks” in early 2011. A survey of a sample of 65 actors from the initial network supported these findings: Only a very small group had accessed the draft directly from the Commission. Most respondents who obtained access to the draft had received it from other actors, highlighting the networked flow of informal information in EU politics. Furthermore, the testing of the hypotheses connecting network positions and the level of informedness indicated that presence in or connections to the Brussels sphere had both advantages for overall access to the draft document and with regard to timing. Methodologically, challenges of both the network analysis and the analysis of information flows but also their relevance for the study of EU politics have been documented. In summary, this study has laid the foundation for a different way to study EU policy-making by connecting topical and methodological elements – such as affiliation network analysis and EU committee governance – which so far have not been considered together, thereby contributing in various ways to political science and EU studies.
For the first time the transcriptional reprogramming of distinct root cortex cells during the arbuscular mycorrhizal (AM) symbiosis was investigated by combining Laser Capture Mirodissection and Affymetrix GeneChip® Medicago genome array hybridization. The establishment of cryosections facilitated the isolation of high quality RNA in sufficient amounts from three different cortical cell types. The transcript profiles of arbuscule-containing cells (arb cells), non-arbuscule-containing cells (nac cells) of Rhizophagus irregularis inoculated Medicago truncatula roots and cortex cells of non-inoculated roots (cor) were successfully explored. The data gave new insights in the symbiosis-related cellular reorganization processes and indicated that already nac cells seem to be prepared for the upcoming fungal colonization. The mycorrhizal- and phosphate-dependent transcription of a GRAS TF family member (MtGras8) was detected in arb cells and mycorrhizal roots. MtGRAS shares a high sequence similarity to a GRAS TF suggested to be involved in the fungal colonization processes (MtRAM1). The function of MtGras8 was unraveled upon RNA interference- (RNAi-) mediated gene silencing. An AM symbiosis-dependent expression of a RNAi construct (MtPt4pro::gras8-RNAi) revealed a successful gene silencing of MtGras8 leading to a reduced arbuscule abundance and a higher proportion of deformed arbuscules in root with reduced transcript levels. Accordingly, MtGras8 might control the arbuscule development and life-time. The targeting of MtGras8 by the phosphate-dependent regulated miRNA5204* was discovered previously (Devers et al., 2011). Since miRNA5204* is known to be affected by phosphate, the posttranscriptional regulation might represent a link between phosphate signaling and arbuscule development. In this work, the posttranscriptional regulation was confirmed by mis-expression of miRNA5204* in M. truncatula roots. The miRNA-mediated gene silencing affects the MtGras8 transcript abundance only in the first two weeks of the AM symbiosis and the mis-expression lines seem to mimic the phenotype of MtGras8-RNAi lines. Additionally, MtGRAS8 seems to form heterodimers with NSP2 and RAM1, which are known to be key regulators of the fungal colonization process (Hirsch et al., 2009; Gobbato et al., 2012). These data indicate that MtGras8 and miRNA5204* are linked to the sym pathway and regulate the arbuscule development in phosphate-dependent manner.
The Semantic Web provides information contained in the World Wide Web as machine-readable facts. In comparison to a keyword-based inquiry, semantic search enables a more sophisticated exploration of web documents. By clarifying the meaning behind entities, search results are more precise and the semantics simultaneously enable an exploration of semantic relationships. However, unlike keyword searches, a semantic entity-focused search requires that web documents are annotated with semantic representations of common words and named entities. Manual semantic annotation of (web) documents is time-consuming; in response, automatic annotation services have emerged in recent years. These annotation services take continuous text as input, detect important key terms and named entities and annotate them with semantic entities contained in widely used semantic knowledge bases, such as Freebase or DBpedia. Metadata of video documents require special attention. Semantic analysis approaches for continuous text cannot be applied, because information of a context in video documents originates from multiple sources possessing different reliabilities and characteristics. This thesis presents a semantic analysis approach consisting of a context model and a disambiguation algorithm for video metadata. The context model takes into account the characteristics of video metadata and derives a confidence value for each metadata item. The confidence value represents the level of correctness and ambiguity of the textual information of the metadata item. The lower the ambiguity and the higher the prospective correctness, the higher the confidence value. The metadata items derived from the video metadata are analyzed in a specific order from high to low confidence level. Previously analyzed metadata are used as reference points in the context for subsequent disambiguation. The contextually most relevant entity is identified by means of descriptive texts and semantic relationships to the context. The context is created dynamically for each metadata item, taking into account the confidence value and other characteristics. The proposed semantic analysis follows two hypotheses: metadata items of a context should be processed in descendent order of their confidence value, and the metadata that pertains to a context should be limited by content-based segmentation boundaries. The evaluation results support the proposed hypotheses and show increased recall and precision for annotated entities, especially for metadata that originates from sources with low reliability. The algorithms have been evaluated against several state-of-the-art annotation approaches. The presented semantic analysis process is integrated into a video analysis framework and has been successfully applied in several projects for the purpose of semantic video exploration of videos.
Passive plant actuators have fascinated many researchers in the field of botany and structural biology since at least one century. Up to date, the most investigated tissue types in plant and artificial passive actuators are fibre-reinforced composites (and multilayered assemblies thereof) where stiff, almost inextensible cellulose microfibrils direct the otherwise isotropic swelling of a matrix. In addition, Nature provides examples of actuating systems based on lignified, low-swelling, cellular solids enclosing a high-swelling cellulosic phase. This is the case of the Delosperma nakurense seed capsule, in which a specialized tissue promotes the reversible opening of the capsule upon wetting. This tissue has a diamond-shaped honeycomb microstructure characterized by high geometrical anisotropy: when the cellulosic phase swells inside this constraining structure, the tissue deforms up to four times in one principal direction while maintaining its original dimension in the other. Inspired by the example of the Delosoperma nakurense, in this thesis we analyze the role of architecture of 2D cellular solids as models for natural hygromorphs. To start off, we consider a simple fluid pressure acting in the cells and try to assess the influence of several architectural parameters onto their mechanical actuation. Since internal pressurization is a configurational type of load (that is the load direction is not fixed but it “follows” the structure as it deforms) it will result in the cellular structure acquiring a “spontaneous” shape. This shape is independent of the load but just depends on the architectural characteristics of the cells making up the structure itself. Whereas regular convex tiled cellular solids (such as hexagonal, triangular or square lattices) deform isotropically upon pressurization, we show through finite element simulations that by introducing anisotropic and non-convex, reentrant tiling large expansions can be achieved in each individual cell. The influence of geometrical anisotropy onto the expansion behaviour of a diamond shaped honeycomb is assessed by FEM calculations and a Born lattice approximation. We found that anisotropic expansions (eigenstrains) comparable to those observed in the keels tissue of the Delosoperma nakurense are possible. In particular these depend on the relative contributions of bending and stretching of the beams building up the honeycomb. Moreover, by varying the walls’ Young modulus E and internal pressure p we found that both the eigenstrains and 2D elastic moduli scale with the ratio p/E. Therefore the potential of these pressurized structures as soft actuators is outlined. This approach was extended by considering several 2D cellular solids based on two types of non-convex cells. Each honeycomb is build as a lattice made of only one non-convex cell. Compared to usual honeycombs, these lattices have kinked walls between neighbouring cells which offers a hidden length scale allowing large directed deformations. By comparing the area expansion in all lattices, we were able to show that less convex cells are prone to achieve larger area expansions, but the direction in which the material expands is variable and depends on the local cell’s connectivity. This has repercussions both at the macroscopic (lattice level) and microscopic (cells level) scales. At the macroscopic scale, these non-convex lattices can experience large anisotropic (similarly to the diamond shaped honeycomb) or perfectly isotropic principal expansions, large shearing deformations or a mixed behaviour. Moreover, lattices that at the macroscopic scale expand similarly can show quite different microscopic deformation patterns that include zig-zag motions and radical changes of the initial cell shape. Depending on the lattice architecture, the microscopic deformations of the individual cells can be equal or not, so that they can build up or mutually compensate and hence give rise to the aforementioned variety of macroscopic behaviours. Interestingly, simple geometrical arguments involving the undeformed cell shape and its local connectivity enable to predict the results of the FE simulations. Motivated by the results of the simulations, we also created experimental 3D printed models of such actuating structures. When swollen, the models undergo substantial deformation with deformation patterns qualitatively following those predicted by the simulations. This work highlights how the internal architecture of a swellable cellular solid can lead to complex shape changes which may be useful in the fields of soft robotics or morphing structures.
An important strand of research has investigated the question of how children acquire a morphological system using offline data from spontaneous or elicited child language. Most of these studies have found dissociations in how children apply regular and irregular inflection (Marcus et al. 1992, Weyerts & Clahsen 1994, Rothweiler & Clahsen 1993). These studies have considerably deepened our understanding of how linguistic knowledge is acquired and organised in the human mind. Their methodological procedures, however, do not involve measurements of how children process morphologically complex forms in real time. To date, little is known about how children process inflected word forms. The aim of this study is to investigate children’s processing of inflected words in a series of on-line reaction time experiments. We used a cross-modal priming experiment to test for decompositional effects on the central level. We used a speeded production task and a lexical decision task to test for frequency effects on access level in production and recognition. Children’s behaviour was compared to adults’ behaviour towards three participle types (-t participles, e.g. getanzt ‘danced’ vs. -n participles with stem change, e.g. gebrochen ‘broken’ vs.-n participles without stem change, e.g. geschlafen ‘slept’). For the central level, results indicate that -t participles but not -n participles have decomposed representations. For the access level, results indicate that -t participles are represented according to their morphemes and additionally as full forms, at least from the age of nine years onwards (Pinker 1999 and Clahsen et al. 2004). Further evidence suggested that -n participles are represented as full-form entries on access level and that -n participles without stem change may encode morphological structure (cf. Clahsen et al. 2003). Out data also suggests that processing strategies for -t participles are differently applied in recognition and production. These results provide evidence that children (within the age range tested) employ the same mechanisms for processing participles as adults. The child lexicon grows as children form additional full-form representations for -t participles on access level and elaborate their full-form lexical representations of -n participles on central level. These results are consistent with processing as explained in dual-system theories.
Measuring the metabolite profile of plants can be a strong phenotyping tool, but the changes of metabolite pool sizes are often difficult to interpret, not least because metabolite pool sizes may stay constant while carbon flows are altered and vice versa. Hence, measuring the carbon allocation of metabolites enables a better understanding of the metabolic phenotype. The main challenge of such measurements is the in vivo integration of a stable or radioactive label into a plant without perturbation of the system. To follow the carbon flow of a precursor metabolite, a method is developed in this work that is based on metabolite profiling of primary metabolites measured with a mass spectrometer preceded by a gas chromatograph (Wagner et al. 2003; Erban et al. 2007; Dethloff et al. submitted). This method generates stable isotope profiling data, besides conventional metabolite profiling data. In order to allow the feeding of a 13C sucrose solution into the plant, a petiole and a hypocotyl feeding assay are developed. To enable the processing of large numbers of single leaf samples, their preparation and extraction are simplified and optimised. The metabolite profiles of primary metabolites are measured, and a simple relative calculation is done to gain information on carbon allocation from 13C sucrose. This method is tested examining single leaves of one rosette in different developmental stages, both metabolically and regarding carbon allocation from 13C sucrose. It is revealed that some metabolite pool sizes and 13C pools are tightly associated to relative leaf growth, i.e. to the developmental stage of the leaf. Fumaric acid turns out to be the most interesting candidate for further studies because pool size and 13C pool diverge considerably. In addition, the analyses are also performed on plants grown in the cold, and the initial results show a different metabolite pool size pattern across single leaves of one Arabidopsis rosette, compared to the plants grown under normal temperatures. Lastly, in situ expression of REIL genes in the cold is examined using promotor-GUS plants. Initial results suggest that single leaf metabolite profiles of reil2 differ from those of the WT.
The habilitation thesis covers theoretical investigations on light-induced processes in molecules. The study is focussed on changes of the molecular electronic structure and geometry, caused either by photoexcitation in the event of a spectroscopic analysis, or by a selective control with shaped laser pulses. The applied and developed methods are predominantly based on quantum chemistry as well as on electron and nuclear quantum dynamics, and in parts on molecular dynamics. The studied scientific problems deal with stereoisomerism and the question of how to either switch or distinguish chiral molecules using laser pulses, and with the essentials for the simulation of the spectroscopic response of biochromophores, in order to unravel their photophysics. The accomplished findings not only explain experimental results and extend existing approaches, but also contribute significantly to the basic understanding of the investigated light-driven molecular processes. The main achievements can be divided in three parts: First, a quantum theory for an enantio- and diastereoselective or, in general, stereoselective laser pulse control was developed and successfully applied to influence the chirality of molecular switches. The proposed axially chiral molecules possess different numbers of "switchable" stable chiral conformations, with one particular switch featuring even a true achiral "off"-state which allows to enantioselectively "turn on" its chirality. Furthermore, surface mounted chiral molecular switches with several well-defined orientations were treated, where a newly devised highly flexible stochastic pulse optimization technique provides high stereoselectivity and efficiency at the same time, even for coupled chirality-changing degrees of freedom. Despite the model character of these studies, the proposed types of chiral molecular switches and, all the more, the developed basic concepts are generally applicable to design laser pulse controlled catalysts for asymmetric synthesis, or to achieve selective changes in the chirality of liquid crystals or in chiroptical nanodevices, implementable in information processing or as data storage. Second, laser-driven electron wavepacket dynamics based on ab initio calculations, namely time-dependent configuration interaction, was extended by the explicit inclusion of magnetic field-magnetic dipole interactions for the simulation of the qualitative and quantitative distinction of enantiomers in mass spectrometry by means of circularly polarized ultrashort laser pulses. The developed approach not only allows to explain the origin of the experimentally observed influence of the pulse duration on the detected circular dichroism in the ion yield, but also to predict laser pulse parameters for an optimal distinction of enantiomers by ultrashort shaped laser pulses. Moreover, these investigations in combination with the previous ones provide a fundamental understanding of the relevance of electric and magnetic interactions between linearly or non-linearly polarized laser pulses and (pro-)chiral molecules for either control by enantioselective excitation or distinction by enantiospecific excitation. Third, for selected light-sensitive biological systems of central importance, like e.g. antenna complexes of photosynthesis, simulations of processes which take place during and after photoexcitation of their chromophores were performed, in order to explain experimental (spectroscopic) findings as well as to understand the underlying photophysical and photochemical principles. In particular, aspects of normal mode mixing due to geometrical changes upon photoexcitation and their impact on (time-dependent) vibronic and resonance Raman spectra, as well as on intramolecular energy redistribution were addressed. In order to explain unresolved experimental findings, a simulation program for the calculation of vibronic and resonance Raman spectra, accounting for changes in both vibrational frequencies and normal modes, was created based on a time-dependent formalism. In addition, the influence of the biochemical environment on the electronic structure of the chromophores was studied by electrostatic interactions and mechanical embedding using hybrid quantum-classical methods. Environmental effects were found to be of importance, in particular, for the excitonic coupling of chromophores in light-harvesting complex II. Although the simulations for such highly complex systems are still restricted by various approximations, the improved approaches and obtained results have proven to be important contributions for a better understanding of light-induced processes in biosystems which also adds to efforts of their artificial reproduction.
When we read a text, we obtain information at different levels of representation from abstract symbols. A reader’s ultimate aim is the extraction of the meaning of the words and the text. The reserach of eye movements in reading covers a broad range of psychological systems, ranging from low-level perceptual and motor processes to high-level cognition. Reading of skilled readers proceeds highly automatic, but is a complex phenomenon of interacting subprocesses at the same time. The study of eye movements during reading offers the possibility to investigate cognition via behavioral measures during the excercise of an everyday task. The process of reading is not limited to the directly fixated (or foveal) word but also extends to surrounding (or parafoveal) words, particularly the word to the right of the gaze position. This process may be unconscious, but parafoveal information is necessary for efficient reading. There is an ongoing debate on whether processing of the upcoming word encompasses word meaning (or semantics) or only superficial features. To increase the knowledge about how the meaning of one word helps processing another word, seven experiments were conducted. In these studies, words were exachanged during reading. The degree of relatedness between the word to the right of the currently fixated one and the word subsequently fixated was experimentally manipulated. Furthermore, the time course of the parafoveal extraction of meaning was investigated with two different approaches, an experimental one and a statistical one. As a major finding, fixation times were consistently lower if a semantically related word was presented compared to the presence of an unrelated word. Introducing an experimental technique that allows controlling the duration for which words are available, the time course of processing and integrating meaning was evaluated. Results indicated both facilitation and inhibition due to relatedness between the meanings of words. In a more natural reading situation, the effectiveness of the processing of parafoveal words was sometimes time-dependent and substantially increased with shorter distances between the gaze position and the word. Findings are discussed with respect to theories of eye-movement control. In summary, the results are more compatible with models of distributed word processing. The discussions moreover extend to language differences and technical issues of reading research.
Landslides are one of the biggest natural hazards in Georgia, a mountainous country in the Caucasus. So far, no systematic monitoring and analysis of the dynamics of landslides in Georgia has been made. Especially as landslides are triggered by extrinsic processes, the analysis of landslides together with precipitation and earthquakes is challenging. In this thesis I describe the advantages and limits of remote sensing to detect and better understand the nature of landslide in Georgia. The thesis is written in a cumulative form, composing a general introduction, three manuscripts and a summary and outlook chapter. In the present work, I measure the surface displacement due to active landslides with different interferometric synthetic aperture radar (InSAR) methods. The slow landslides (several cm per year) are well detectable with two-pass interferometry. In same time, the extremely slow landslides (several mm per year) could be detected only with time series InSAR techniques. I exemplify the success of InSAR techniques by showing hitherto unknown landslides, located in the central part of Georgia. Both, the landslide extent and displacement rate is quantified. Further, to determine a possible depth and position of potential sliding planes, inverse models were developed. Inverse modeling searches for parameters of source which can create observed displacement distribution. I also empirically estimate the volume of the investigated landslide using displacement distributions as derived from InSAR combined with morphology from an aerial photography. I adapted a volume formula for our case, and also combined available seismicity and precipitation data to analyze potential triggering factors. A governing question was: What causes landslide acceleration as observed in the InSAR data? The investigated area (central Georgia) is seismically highly active. As an additional product of the InSAR data analysis, a deformation area associated with the 7th September Mw=6.0 earthquake was found. Evidences of surface ruptures directly associated with the earthquake could not be found in the field, however, during and after the earthquake new landslides were observed. The thesis highlights that deformation from InSAR may help to map area prone landslides triggering by earthquake, potentially providing a technique that is of relevance for country wide landslide monitoring, especially as new satellite sensors will emerge in the coming years.
Constraints allow developers to specify desired properties of systems in a number of domains, and have those properties be maintained automatically. This results in compact, declarative code, avoiding scattered code to check and imperatively re-satisfy invariants. Despite these advantages, constraint programming is not yet widespread, with standard imperative programming still the norm. There is a long history of research on integrating constraint programming with the imperative paradigm. However, this integration typically does not unify the constructs for encapsulation and abstraction from both paradigms. This impedes re-use of modules, as client code written in one paradigm can only use modules written to support that paradigm. Modules require redundant definitions if they are to be used in both paradigms. We present a language – Babelsberg – that unifies the constructs for en- capsulation and abstraction by using only object-oriented method definitions for both declarative and imperative code. Our prototype – Babelsberg/R – is an extension to Ruby, and continues to support Ruby’s object-oriented se- mantics. It allows programmers to add constraints to existing Ruby programs in incremental steps by placing them on the results of normal object-oriented message sends. It is implemented by modifying a state-of-the-art Ruby virtual machine. The performance of standard object-oriented code without con- straints is only modestly impacted, with typically less than 10% overhead compared with the unmodified virtual machine. Furthermore, our architec- ture for adding multiple constraint solvers allows Babelsberg to deal with constraints in a variety of domains. We argue that our approach provides a useful step toward making con- straint solving a generic tool for object-oriented programmers. We also provide example applications, written in our Ruby-based implementation, which use constraints in a variety of application domains, including interactive graphics, circuit simulations, data streaming with both hard and soft constraints on performance, and configuration file Management.
In this work, the development of temperature- and protein-responsive sensor materials based on biocompatible, inverse hydrogel opals (IHOs) is presented. With these materials, large biomolecules can be specifically recognised and the binding event visualised. The preparation of the IHOs was performed with a template process, for which monodisperse silica particles were vertically deposited onto glass slides as the first step. The obtained colloidal crystals with a thickness of 5 μm displayed opalescent reflections because of the uniform alignment of the colloids. As a second step, the template was embedded in a matrix consisting of biocompatible, thermoresponsive hydrogels. The comonomers were selected from the family of oligo(ethylene glycol)methacrylates. The monomer solution was injected into a polymerisation mould, which contained the colloidal crystals as a template. The space in-between the template particles was filled with the monomer solution and the hydrogel was cured via UV-polymerisation. The particles were chemically etched, which resulted in a porous inner structure. The uniform alignment of the pores and therefore the opalescent reflection were maintained, so these system were denoted as inverse hydrogel opals. A pore diameter of several hundred nanometres as well as interconnections between the pores should facilitate a diffusion of bigger (bio)molecules, which was always a challenge in the presented systems until now. The copolymer composition was chosen to result in a hydrogel collapse over 35 °C. All hydrogels showed pronounced swelling in water below the critical temperature. The incorporation of a reactive monomer with hydroxyl groups ensured a potential coupling group for the introduction of recognition units for analytes, e.g. proteins. As a test system, biotin as a recognition unit for avidin was coupled to the IHO via polymer-analogous Steglich esterification. The amount of accessible biotin was quantified with a colorimetric binding assay. When avidin was added to the biotinylated IHO, the wavelength of the opalescent reflection was significantly shifted and therefore the binding event was visualised. This effect is based on the change in swelling behaviour of the hydrogel after binding of the hydrophilic avidin, which is amplified by the thermoresponsive nature of the hydrogel. A swelling or shrinking of the pores induces a change in distance of the crystal planes, which are responsible for the colour of the reflection. With these findings, the possibility of creating sensor materials or additional biomolecules in the size range of avidin is given.
Numerical simulations of galaxy formation and observational Galactic Astronomy are two fields of research that study the same objects from different perspectives. Simulations try to understand galaxies like our Milky Way from an evolutionary point of view while observers try to disentangle the current structure and the building blocks of our Galaxy. Due to great advances in computational power as well as in massive stellar surveys we are now able to compare resolved stellar populations in simulations and in observations. In this thesis we use a number of approaches to relate the results of the two fields to each other. The major observational data set we refer to for this work comes from the Radial Velocity Experiment (RAVE), a massive spectroscopic stellar survey that observed almost half a million stars in the Galaxy. In a first study we use three different models of the Galaxy to generate synthetic stellar surveys that can be directly compared to the RAVE data. To do this we evaluate the RAVE selection function to great detail. Among the Galaxy models is the widely used Besancon model that performs well when individual parameter distribution are considered, but fails when we study chemodynamic correlations. The other two models are based on distributions of mass particles instead of analytical distribution functions. This is the first time that such models are converted to the space of observables and are compared to a stellar survey. We show that these models can be competitive and in some aspects superior to analytic models, because of their self-consistent dynamic history. In the case of a full cosmological simulation of disk galaxy formation we can recover features in the synthetic survey that relate to the known issues of the model and hence proof that our technique is sensitive to the global structure of the model. We argue that the next generation of cosmological galaxy formation simulations will deliver valuable models for our Galaxy. Testing these models with our approach will provide a direct connection between stellar Galactic astronomy and physical cosmology. In the second part of the thesis we use a sample of high-velocity halo stars from the RAVE data to estimate the Galactic escape speed and the virial mass of the Milky Way. In the course of this study cosmological simulations of galaxy formation also play a crucial role. Here we use them to calibrate and extensively test our analysis technique. We find the local Galactic escape speed to be 533 (+54/-41) km/s (90% confidence). With this result in combination with a simple mass model of the Galaxy we then construct an estimate of the virial mass of the Galaxy. For the mass profile of the dark matter halo we use two extreme models, a pure Navarro, Frenk & White (NFW) profile and an adiabatically contracted NFW profile. When we use statistics on the concentration parameter of these profile taken from large dissipationless cosmological simulations we obtain an estimate of the virial mass that is almost independent of the choice of the halo profile. For the mass M_340 enclosed within R_340 = 180 kpc we find 1.3 (+0.4/-0.3) x 10^12 M_sun. This value is in very good agreement with a number of other mass estimates in the literature that are based on independent data sets and analysis techniques. In the last part of this thesis we investigate a new possible channel to generate a population of Hypervelocity stars (HVSs) that is observed in the stellar halo. Commonly, it is assumed that the velocities of these stars originate from an interaction with the super-massive black hole in the Galactic center. It was suggested recently that stars stripped-off a disrupted satellite galaxy could reach similar velocities and leave the Galaxy. Here we study in detail the kinematics of tidal debris stars to investigate the probability that the observed sample of HVSs could partly originate from such a galaxy collision. We use a suite of $N$-body simulations following the encounter of a satellite galaxy with its Milky Way-type host galaxy. We quantify the typical pattern in angular and phase space formed by the debris stars and develop a simple model that predicts the kinematics of stripped-off stars. We show that the distribution of orbital energies in the tidal debris has a typical form that can be described quite accurately by a simple function. The main parameters determining the maximum energy kick a tidal debris star can get is the initial mass of the satellite and only to a lower extent its orbit. Main contributors to an unbound stellar population created in this way are massive satellites (M_sat > 10^9 M_sun). The probability that the observed HVS population is significantly contaminated by tidal debris stars appears small in the light of our results.
Public debate about energy relations between the EU and Russia is distorted. These distortions present considerable obstacles to the development of true partnership. At the core of the conflict is a struggle for resource rents between energy producing, energy consuming and transit countries. Supposed secondary aspects, however, are also of great importance. They comprise of geopolitics, market access, economic development and state sovereignty. The European Union, having engaged in energy market liberalisation, faces a widening gap between declining domestic resources and continuously growing energy demand. Diverse interests inside the EU prevent the definition of a coherent and respected energy policy. Russia, for its part, is no longer willing to subsidise its neighbouring economies by cheap energy exports. The Russian government engages in assertive policies pursuing Russian interests. In so far, it opts for a different globalisation approach, refusing the role of mere energy exporter. In view of the intensifying struggle for global resources, Russia, with its large energy potential, appears to be a very favourable option for European energy supplies, if not the best one. However, several outcomes of the strategic game between the two partners can be imagined. Engaging in non-cooperative strategies will in the end leave all stakeholders worse-off. The European Union should therefore concentrate on securing its partnership with Russia instead of damaging it. Stable cooperation would need the acceptance that the partner may pursue his own goals, which might be different from one’s own interests. The question is, how can a sustainable compromise be found? This thesis finds that a mix of continued dialogue, a tit for tat approach bolstered by an international institutional framework and increased integration efforts appears as a preferable solution.
Challenging Khmer citizenship : minorities, the state, and the international community in Cambodia
(2013)
The idea of a distinctly ‘liberal’ form of multiculturalism has emerged in the theory and practice of Western democracies and the international community has become actively engaged in its global dissemination via international norms and organizations. This thesis investigates the internationalization of minority rights, by exploring state-minority relations in Cambodia, in light of Will Kymlicka’s theory of multicultural citizenship. Based on extensive empirical research, the analysis explores the situation and aspirations of Cambodia’s ethnic Vietnamese, highland peoples, Muslim Cham, ethnic Chinese and Lao and the relationships between these groups and the state. All Cambodian regimes since independence have defined citizenship with reference to the ethnicity of the Khmer majority and have - often violently - enforced this conception through the assimilation of highland peoples and the Cham and the exclusion of ethnic Vietnamese and Chinese. Cambodia’s current constitution, too, defines citizenship ethnically. State-sponsored Khmerization systematically privileges members of the majority culture and marginalizes minority members politically, economically and socially. The thesis investigates various international initiatives aimed at promoting application of minority rights norms in Cambodia. It demonstrates that these initiatives have largely failed to accomplish a greater degree of compliance with international norms in practice. This failure can be explained by a number of factors, among them Cambodia’s neo-patrimonial political system, the geo-political fears of a ‘minoritized’ Khmer majority, the absence of effective regional security institutions, the lack of minority access to political decision-making, the significant differences between international and Cambodian conceptions of modern statehood and citizenship and the emergence of China as Cambodia’s most important bilateral donor and investor. Based on this analysis, the dissertation develops recommendations for a sequenced approach to minority rights promotion, with pragmatic, less ambitious shorter-term measures that work progressively towards achievement of international norms in the longer-term.
Requirements engineers have to elicit, document, and validate how stakeholders act and interact to achieve their common goals in collaborative scenarios. Only after gathering all information concerning who interacts with whom to do what and why, can a software system be designed and realized which supports the stakeholders to do their work. To capture and structure requirements of different (groups of) stakeholders, scenario-based approaches have been widely used and investigated. Still, the elicitation and validation of requirements covering collaborative scenarios remains complicated, since the required information is highly intertwined, fragmented, and distributed over several stakeholders. Hence, it can only be elicited and validated collaboratively. In times of globally distributed companies, scheduling and conducting workshops with groups of stakeholders is usually not feasible due to budget and time constraints. Talking to individual stakeholders, on the other hand, is feasible but leads to fragmented and incomplete stakeholder scenarios. Going back and forth between different individual stakeholders to resolve this fragmentation and explore uncovered alternatives is an error-prone, time-consuming, and expensive task for the requirements engineers. While formal modeling methods can be employed to automatically check and ensure consistency of stakeholder scenarios, such methods introduce additional overhead since their formal notations have to be explained in each interaction between stakeholders and requirements engineers. Tangible prototypes as they are used in other disciplines such as design, on the other hand, allow designers to feasibly validate and iterate concepts and requirements with stakeholders. This thesis proposes a model-based approach for prototyping formal behavioral specifications of stakeholders who are involved in collaborative scenarios. By simulating and animating such specifications in a remote domain-specific visualization, stakeholders can experience and validate the scenarios captured so far, i.e., how other stakeholders act and react. This interactive scenario simulation is referred to as a model-based virtual prototype. Moreover, through observing how stakeholders interact with a virtual prototype of their collaborative scenarios, formal behavioral specifications can be automatically derived which complete the otherwise fragmented scenarios. This, in turn, enables requirements engineers to elicit and validate collaborative scenarios in individual stakeholder sessions – decoupled, since stakeholders can participate remotely and are not forced to be available for a joint session at the same time. This thesis discusses and evaluates the feasibility, understandability, and modifiability of model-based virtual prototypes. Similarly to how physical prototypes are perceived, the presented approach brings behavioral models closer to being tangible for stakeholders and, moreover, combines the advantages of joint stakeholder sessions and decoupled sessions.
In the presence of a solid-liquid or liquid-air interface, bacteria can choose between a planktonic and a sessile lifestyle. Depending on environmental conditions, cells swimming in close proximity to the interface can irreversibly attach to the surface and grow into three-dimensional aggregates where the majority of cells is sessile and embedded in an extracellular polymer matrix (biofilm). We used microfluidic tools and time lapse microscopy to perform experiments with the polarly flagellated soil bacterium Pseudomonas putida (P. putida), a bacterial species that is able to form biofilms. We analyzed individual trajectories of swimming cells, both in the bulk fluid and in close proximity to a glass-liquid interface. Additionally, surface related growth during the early phase of biofilm formation was investigated. In the bulk fluid, P.putida shows a typical bacterial swimming pattern of alternating periods of persistent displacement along a line (runs) and fast reorientation events (turns) and cells swim with an average speed around 24 micrometer per second. We found that the distribution of turning angles is bimodal with a dominating peak around 180 degrees. In approximately six out of ten turning events, the cell reverses its swimming direction. In addition, our analysis revealed that upon a reversal, the cell systematically changes its swimming speed by a factor of two on average. Based on the experimentally observed values of mean runtime and rotational diffusion, we presented a model to describe the spreading of a population of cells by a run-reverse random walker with alternating speeds. We successfully recover the mean square displacement and, by an extended version of the model, also the negative dip in the directional autocorrelation function as observed in the experiments. The analytical solution of the model demonstrates that alternating speeds enhance a cells ability to explore its environment as compared to a bacterium moving at a constant intermediate speed. As compared to the bulk fluid, for cells swimming near a solid boundary we observed an increase in swimming speed at distances below d= 5 micrometer and an increase in average angular velocity at distances below d= 4 micrometer. While the average speed was maximal with an increase around 15% at a distance of d= 3 micrometer, the angular velocity was highest in closest proximity to the boundary at d=1 micrometer with an increase around 90% as compared to the bulk fluid. To investigate the swimming behavior in a confinement between two solid boundaries, we developed an experimental setup to acquire three-dimensional trajectories using a piezo driven objective mount coupled to a high speed camera. Results on speed and angular velocity were consistent with motility statistics in the presence of a single boundary. Additionally, an analysis of the probability density revealed that a majority of cells accumulated near the upper and lower boundaries of the microchannel. The increase in angular velocity is consistent with previous studies, where bacteria near a solid boundary were shown to swim on circular trajectories, an effect which can be attributed to a wall induced torque. The increase in speed at a distance of several times the size of the cell body, however, cannot be explained by existing theories which either consider the drag increase on cell body and flagellum near a boundary (resistive force theory) or model the swimming microorganism by a multipole expansion to account for the flow field interaction between cell and boundary. An accumulation of swimming bacteria near solid boundaries has been observed in similar experiments. Our results confirm that collisions with the surface play an important role and hydrodynamic interactions alone cannot explain the steady-state accumulation of cells near the channel walls. Furthermore, we monitored the number growth of cells in the microchannel under medium rich conditions. We observed that, after a lag time, initially isolated cells at the surface started to grow by division into colonies of increasing size, while coexisting with a comparable smaller number of swimming cells. After 5:50 hours, we observed a sudden jump in the number of swimming cells, which was accompanied by a breakup of bigger clusters on the surface. After approximately 30 minutes where planktonic cells dominated in the microchannel, individual swimming cells reattached to the surface. We interpret this process as an emigration and recolonization event. A number of complementary experiments were performed to investigate the influence of collective effects or a depletion of the growth medium on the transition. Similar to earlier observations on another bacterium from the same family we found that the release of cells to the swimming phase is most likely the result of an individual adaption process, where syntheses of proteins for flagellar motility are upregulated after a number of division cycles at the surface.
Logging and large earthquakes are disturbances that may significantly affect hydrological and erosional processes and process rates, although in decisively different ways. Despite numerous studies that have documented the impacts of both deforestation and earthquakes on water and sediment fluxes, a number of details regarding the timing and type of de- and reforestation; seismic impacts on subsurface water fluxes; or the overall geomorphic work involved have remained unresolved. The main objective of this thesis is to address these shortcomings and to better understand and compare the hydrological and erosional process responses to such natural and man-made disturbances. To this end, south-central Chile provides an excellent natural laboratory owing to its high seismicity and the ongoing conversion of land into highly productive plantation forests. In this dissertation I combine paired catchment experiments, data analysis techniques, and physics-based modelling to investigate: 1) the effect of plantation forests on water resources, 2) the source and sink behavior of timber harvest areas in terms of overland flow generation and sediment fluxes, 3) geomorphic work and its efficiency as a function of seasonal logging, 4) possible hydrologic responses of the saturated zone to the 2010 Maule earthquake and 5) responses of the vadose zone to this earthquake. Re 1) In order to quantify the hydrologic impact of plantation forests, it is fundamental to first establish their water balances. I show that tree species is not significant in this regard, i.e. Pinus radiata and Eucalyptus globulus do not trigger any decisive different hydrologic response. Instead, water consumption is more sensitive to soil-water supply for the local hydro-climatic conditions. Re 2) Contradictory opinions exist about whether timber harvest areas (THA) generate or capture overland flow and sediment. Although THAs contribute significantly to hydrology and sediment transport because of their spatial extent, little is known about the hydrological and erosional processes occurring on them. I show that THAs may act as both sources and sinks for overland flow, which in turn intensifies surface erosion. Above a rainfall intensity of ~20 mm/h, which corresponds to <10% of all rainfall, THAs may generate runoff whereas below that threshold they remain sinks. The overall contribution of Hortonian runoff is thus secondary considering the local rainfall regime. The bulk of both runoff and sediment is generated by Dunne, saturation excess, overland flow. I also show that logging may increase infiltrability on THAs which may cause an initial decrease in streamflow followed by an increase after the groundwater storage has been refilled. Re 3) I present changes in frequency-magnitude distributions following seasonal logging by applying Quantile Regression Forests at hitherto unprecedented detail. It is clearly the season that controls the hydro-geomorphic work efficiency of clear cutting. Logging, particularly dry seasonal logging, caused a shift of work efficiency towards less flashy and mere but more frequent moderate rainfall-runoff events. The sediment transport is dominated by Dunne overland flow which is consistent with physics-based modelling using WASA-SED. Re 4) It is well accepted that earthquakes may affect hydrological processes in the saturated zone. Assuming such flow conditions, consolidation of saturated saprolitic material is one possible response. Consolidation raises the hydraulic gradients which may explain the observed increase in discharge following earthquakes. By doing so, squeezed water saturates the soil which in turn increases the water accessible for plant transpiration. Post-seismic enhanced transpiration is reflected in the intensification of diurnal cycling. Re 5) Assuming unsaturated conditions, I present the first evidence that the vadose zone may also respond to seismic waves by releasing pore water which in turn feeds groundwater reservoirs. By doing so, water tables along the valley bottoms are elevated thus providing additional water resources to the riparian vegetation. By inverse modelling, the transient increase in transpiration is found to be 30-60%. Based on the data available, both hypotheses, are not testable. Finally, when comparing the hydrological and erosional effects of the Maule earthquake with the impact of planting exotic plantation forests, the overall observed earthquake effects are comparably small, and limited to short time scales.
Systems of Systems (SoS) have received a lot of attention recently. In this thesis we will focus on SoS that are built atop the techniques of Service-Oriented Architectures and thus combine the benefits and challenges of both paradigms. For this thesis we will understand SoS as ensembles of single autonomous systems that are integrated to a larger system, the SoS. The interesting fact about these systems is that the previously isolated systems are still maintained, improved and developed on their own. Structural dynamics is an issue in SoS, as at every point in time systems can join and leave the ensemble. This and the fact that the cooperation among the constituent systems is not necessarily observable means that we will consider these systems as open systems. Of course, the system has a clear boundary at each point in time, but this can only be identified by halting the complete SoS. However, halting a system of that size is practically impossible. Often SoS are combinations of software systems and physical systems. Hence a failure in the software system can have a serious physical impact what makes an SoS of this kind easily a safety-critical system. The contribution of this thesis is a modelling approach that extends OMG's SoaML and basically relies on collaborations and roles as an abstraction layer above the components. This will allow us to describe SoS at an architectural level. We will also give a formal semantics for our modelling approach which employs hybrid graph-transformation systems. The modelling approach is accompanied by a modular verification scheme that will be able to cope with the complexity constraints implied by the SoS' structural dynamics and size. Building such autonomous systems as SoS without evolution at the architectural level --- i. e. adding and removing of components and services --- is inadequate. Therefore our approach directly supports the modelling and verification of evolution.
Organic semiconductors combine the benefits of organic materials, i.e., low-cost production, mechanical flexibility, lightweight, and robustness, with the fundamental semiconductor properties light absorption, emission, and electrical conductivity. This class of material has several advantages over conventional inorganic semiconductors that have led, for instance, to the commercialization of organic light-emitting diodes which can nowadays be found in the displays of TVs and smartphones. Moreover, organic semiconductors will possibly lead to new electronic applications which rely on the unique mechanical and electrical properties of these materials. In order to push the development and the success of organic semiconductors forward, it is essential to understand the fundamental processes in these materials. This thesis concentrates on understanding how the charge transport in thiophene-based semiconductor layers depends on the layer morphology and how the charge transport properties can be intentionally modified by doping these layers with a strong electron acceptor. By means of optical spectroscopy, the layer morphologies of poly(3-hexylthiophene), P3HT, P3HT-fullerene bulk heterojunction blends, and oligomeric polyquaterthiophene, oligo-PQT-12, are studied as a function of temperature, molecular weight, and processing conditions. The analyses rely on the decomposition of the absorption contributions from the ordered and the disordered parts of the layers. The ordered-phase spectra are analyzed using Spano’s model. It is figured out that the fraction of aggregated chains and the interconnectivity of these domains is fundamental to a high charge carrier mobility. In P3HT layers, such structures can be grown with high-molecular weight, long P3HT chains. Low and medium molecular weight P3HT layers do also contain a significant amount of chain aggregates with high intragrain mobility; however, intergranular connectivity and, therefore, efficient macroscopic charge transport are absent. In P3HT-fullerene blend layers, a highly crystalline morphology that favors the hole transport and the solar cell efficiency can be induced by annealing procedures and the choice of a high-boiling point processing solvent. Based on scanning near-field and polarization optical microscopy, the morphology of oligo-PQT-12 layers is found to be highly crystalline which explains the rather high field-effect mobility in this material as compared to low molecular weight polythiophene fractions. On the other hand, crystalline dislocations and grain boundaries are identified which clearly limit the charge carrier mobility in oligo-PQT-12 layers. The charge transport properties of organic semiconductors can be widely tuned by molecular doping. Indeed, molecular doping is a key to highly efficient organic light-emitting diodes and solar cells. Despite this vital role, it is still not understood how mobile charge carriers are induced into the bulk semiconductor upon the doping process. This thesis contains a detailed study of the doping mechanism and the electrical properties of P3HT layers which have been p-doped by the strong molecular acceptor tetrafluorotetracyanoquinodimethane, F4TCNQ. The density of doping-induced mobile holes, their mobility, and the electrical conductivity are characterized in a broad range of acceptor concentrations. A long-standing debate on the nature of the charge transfer between P3HT and F4TCNQ is resolved by showing that almost every F4TCNQ acceptor undergoes a full-electron charge transfer with a P3HT site. However, only 5% of these charge transfer pairs can dissociate and induce a mobile hole into P3HT which contributes electrical conduction. Moreover, it is shown that the left-behind F4TCNQ ions broaden the density-of-states distribution for the doping-induced mobile holes, which is due to the longrange Coulomb attraction in the low-permittivity organic semiconductors.
Small eye movements during fixation : the case of postsaccadic fixation and preparatory influences
(2013)
Describing human eye movement behavior as an alternating sequence of saccades and fixations turns out to be an oversimplification because the eyes continue to move during fixation. Small-amplitude saccades (e.g., microsaccades) are typically observed 1-2 times per second during fixation. Research on microsaccades came in two waves. Early studies on microsaccades were dominated by the question whether microsaccades affect visual perception, and by studies on the role of microsaccades in the process of fixation control. The lack of evidence for a unique role of microsaccades led to a very critical view on the importance of microsaccades. Over the last years, microsaccades moved into focus again, revealing many interactions with perception, oculomotor control and cognition, as well as intriguing new insights into the neurophysiological implementation of microsaccades. In contrast to early studies on microsaccades, recent findings on microsaccades were accompanied by the development of models of microsaccade generation. While the exact generating mechanisms vary between the models, they still share the assumption that microsaccades are generated in a topographically organized saccade motor map that includes a representation for small-amplitude saccades in the center of the map (with its neurophysiological implementation in the rostral pole of the superior colliculus). In the present thesis I criticize that models of microsaccade generation are exclusively based on results obtained during prolonged presaccadic fixation. I argue that microsaccades should also be studied in a more natural situation, namely the fixation following large saccadic eye movements. Studying postsaccadic fixation offers a new window to falsify models that aim to account for the generation of small eye movements. I demonstrate that error signals (visual and extra-retinal), as well as non-error signals like target eccentricity influence the characteristics of small-amplitude eye movements. These findings require a modification of a model introduced by Rolfs, Kliegl and Engbert (2008) in order to account for the generation of small-amplitude saccades during postsaccadic fixation. Moreover, I present a promising type of survival analysis that allowed me to examine time-dependent influences on postsaccadic eye movements. In addition, I examined the interplay of postsaccadic eye movements and postsaccadic location judgments, highlighting the need to include postsaccadic eye movements as covariate in the analyses of location judgments in the presented paradigm. In a second goal, I tested model predictions concerning preparatory influences on microsaccade generation during presaccadic fixation. The observation, that the preparatory set significantly influenced microsaccade rate, supports the critical model assumption that increased fixation-related activity results in a larger number of microsaccades. In the present thesis I present important influences on the generation of small-amplitude saccades during fixation. These eye movements constitute a rich oculomotor behavior which still poses many research questions. Certainly, small-amplitude saccades represent an interesting source of information and will continue to influence future studies on perception and cognition.
The Arctic tundra, covering approx. 5.5 % of the Earth’s land surface, is one of the last ecosystems remaining closest to its untouched condition. Remote sensing is able to provide information at regular time intervals and large spatial scales on the structure and function of Arctic ecosystems. But almost all natural surfaces reveal individual anisotropic reflectance behaviors, which can be described by the bidirectional reflectance distribution function (BRDF). This effect can cause significant changes in the measured surface reflectance depending on solar illumination and sensor viewing geometries. The aim of this thesis is the hyperspectral and spectro-directional reflectance characterization of important Arctic tundra vegetation communities at representative Siberian and Alaskan tundra sites as basis for the extraction of vegetation parameters, and the normalization of BRDF effects in off-nadir and multi-temporal remote sensing data. Moreover, in preparation for the upcoming German EnMAP (Environmental Mapping and Analysis Program) satellite mission, the understanding of BRDF effects in Arctic tundra is essential for the retrieval of high quality, consistent and therefore comparable datasets. The research in this doctoral thesis is based on field spectroscopic and field spectro-goniometric investigations of representative Siberian and Alaskan measurement grids. The first objective of this thesis was the development of a lightweight, transportable, and easily managed field spectro-goniometer system which nevertheless provides reliable spectro-directional data. I developed the Manual Transportable Instrument platform for ground-based Spectro-directional observations (ManTIS). The outcome of the field spectro-radiometrical measurements at the Low Arctic study sites along important environmental gradients (regional climate, soil pH, toposequence, and soil moisture) show that the different plant communities can be distinguished by their nadir-view reflectance spectra. The results especially reveal separation possibilities between the different tundra vegetation communities in the visible (VIS) blue and red wavelength regions. Additionally, the near-infrared (NIR) shoulder and NIR reflectance plateau, despite their relatively low values due to the low structure of tundra vegetation, are still valuable information sources and can separate communities according to their biomass and vegetation structure. In general, all different tundra plant communities show: (i) low maximum NIR reflectance; (ii) a weakly or nonexistent visible green reflectance peak in the VIS spectrum; (iii) a narrow “red-edge” region between the red and NIR wavelength regions; and (iv) no distinct NIR reflectance plateau. These common nadir-view reflectance characteristics are essential for the understanding of the variability of BRDF effects in Arctic tundra. None of the analyzed tundra communities showed an even closely isotropic reflectance behavior. In general, tundra vegetation communities: (i) usually show the highest BRDF effects in the solar principal plane; (ii) usually show the reflectance maximum in the backward viewing directions, and the reflectance minimum in the nadir to forward viewing directions; (iii) usually have a higher degree of reflectance anisotropy in the VIS wavelength region than in the NIR wavelength region; and (iv) show a more bowl-shaped reflectance distribution in longer wavelength bands (>700 nm). The results of the analysis of the influence of high sun zenith angles on the reflectance anisotropy show that with increasing sun zenith angles, the reflectance anisotropy changes to azimuthally symmetrical, bowl-shaped reflectance distributions with the lowest reflectance values in the nadir view position. The spectro-directional analyses also show that remote sensing products such as the NDVI or relative absorption depth products are strongly influenced by BRDF effects, and that the anisotropic characteristics of the remote sensing products can significantly differ from the observed BRDF effects in the original reflectance data. But the results further show that the NDVI can minimize view angle effects relative to the contrary spectro-directional effects in the red and NIR bands. For the researched tundra plant communities, the overall difference of the off-nadir NDVI values compared to the nadir value increases with increasing sensor viewing angles, but on average never exceeds 10 %. In conclusion, this study shows that changes in the illumination-target-viewing geometry directly lead to an altering of the reflectance spectra of Arctic tundra communities according to their object-specific BRDFs. Since the different tundra communities show only small, but nonetheless significant differences in the surface reflectance, it is important to include spectro-directional reflectance characteristics in the algorithm development for remote sensing products.
The supercapacitor is one of the most important energy storage devices as its construction allows for addressing many of the drawbacks related to batteries, but the low energy density of current systems is a major issue. In this doctoral dissertation, with a view to attaining high energy density supercapacitor systems that can be comparable to those for batteries, new heteroatom-containing carbons in the form of particles and three-dimensional films were investigated. A nitrogen-containing material, acrodam, was chosen as the carbon precursor due to the inexpensiveness, high carbonization yield, oligomerizability, etc. The carbon particles were prepared from acrodam together with caesium acetate as a meltable flux agent, and disclosed excellent properties in hydroquinone-loaded sulphuric acid electrolyte with high energy densities (up to 133.0 Wh kg–1) and sufficient cycle stabilities. These properties are already now comparable to those of batteries. Besides, conductive carbon three-dimensional films were fabricated using acrodam oligomer as the precursor by the inexpensive spin coating method. The films were found to be homogeneous, flat, void- and crack-free, and high conductivities (up to 334 S cm–1) could be obtained at the carbonization temperature of 1000 ºC. Furthermore, a porous carbon three-dimensional film could be formed using an organic template at the first attempt. This finding demonstrates the film’s potentiality for various applications such as supercapacitor electrode; the essential absence of contact resistance within the network should contribute to effective transportation of electron within the electrode. The progress made in this dissertation will open a new way to further enhancement of energy density for supercapacitor as well as other applications that exceeds the current properties.