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This study investigates whether number dissimilarities on subject and object DPs facilitate the comprehension of subject-and object-extracted centre-embedded relative clauses in children with Grammatical Specific Language Impairment (G-SLI). We compared the performance of a group of English-speaking children with G-SLI (mean age: 12; 11) with that of two groups of younger typically developing (TD) children, matched on grammar and receptive vocabulary, respectively. All groups were more accurate on subject-extracted relative clauses than object-extracted ones and, crucially, they all showed greater accuracy for sentences with dissimilar number features (i.e., one singular, one plural) on the head noun and the embedded DP. These findings are interpreted in the light of current psycholinguistic models of sentence comprehension in TD children and provide further insight into the linguistic nature of G-SLI.
Two experiments tested how faithfully German children aged 4; 5 to 5; 6 reproduce ditransitive sentences that are unmarked or marked with respect to word order and focus (Exp1) or definiteness (Exp2). Adopting an optimality theory (OT) approach, it is assumed that in the German adult grammar word order is ranked lower than focus and definiteness. Faithfulness of children's reproductions decreased as markedness of inputs increased; unmarked structures were reproduced most faithfully and unfaithful outputs had most often an unmarked form. Consistent with the OT proposal, children were more tolerant against inputs marked for word order than for focus; in conflict with the proposal, children were less tolerant against inputs marked for word order than for definiteness. Our results suggest that the linearization of objects in German double object constructions is affected by focus and definiteness, but that prosodic principles may have an impact on the position of a focused constituent.
Masked priming research with late (non-native) bilinguals has reported facilitation effects following morphologically derived prime words (scanner - scan). However, unlike for native speakers, there are suggestions that purely orthographic prime-target overlap (scandal - scan) also produces priming in non-native visual word recognition. Our study directly compares orthographically related and derived prime-target pairs. While native readers showed morphological but not formal overlap priming, the two prime types yielded the same magnitudes of facilitation for non-natives. We argue that early word recognition processes in a non-native language are more influenced by surface-form properties than in one's native language.
In the aftermath of the severe flooding in Central Europe in August 2002, a number of changes in flood policies were launched in Germany and other European countries, aiming at improved risk management. The question arises as to whether these changes have already had an impact on the residents' ability to cope with floods, and whether flood-affected private households are now better prepared than they were in 2002. Therefore, computer-aided telephone interviews with private households in Germany that suffered from property damage due to flooding in 2005, 2006, 2010 or 2011 were performed and analysed with respect to flood awareness, precaution, preparedness and recovery. The data were compared to a similar investigation conducted after the flood in 2002.
After the flood in 2002, the level of private precautions taken increased considerably. One contributing factor is the fact that, in general, a larger proportion of people knew that they were at risk of flooding. The best level of precaution was found before the flood events in 2006 and 2011. The main reason for this might be that residents had more experience with flooding than residents affected in 2005 or 2010. Yet, overall, flood experience and knowledge did not necessarily result in building retrofitting or flood-proofing measures, which are considered as mitigating damages most effectively. Hence, investments still need to be stimulated in order to reduce future damage more efficiently.
Early warning and emergency responses were substantially influenced by flood characteristics. In contrast to flood-affected people in 2006 or 2011, people affected by flooding in 2005 or 2010 had to deal with shorter lead times and therefore had less time to take emergency measures. Yet, the lower level of emergency measures taken also resulted from the people's lack of flood experience and insufficient knowledge of how to protect themselves. Overall, it was noticeable that these residents suffered from higher losses. Therefore, it is important to further improve early warning systems and communication channels, particularly in hilly areas with rapid-onset flooding.
Extreme weather events are likely to occur more often under climate change and the resulting effects on ecosystems could lead to a further acceleration of climate change. But not all extreme weather events lead to extreme ecosystem response. Here, we focus on hazardous ecosystem behaviour and identify coinciding weather conditions. We use a simple probabilistic risk assessment based on time series of ecosystem behaviour and climate conditions. Given the risk assessment terminology, vulnerability and risk for the previously defined hazard are estimated on the basis of observed hazardous ecosystem behaviour.
We apply this approach to extreme responses of terrestrial ecosystems to drought, defining the hazard as a negative net biome productivity over a 12-month period. We show an application for two selected sites using data for 1981-2010 and then apply the method to the pan-European scale for the same period, based on numerical modelling results (LPJmL for ecosystem behaviour; ERA-Interim data for climate).
Our site-specific results demonstrate the applicability of the proposed method, using the SPEI to describe the climate condition. The site in Spain provides an example of vulnerability to drought because the expected value of the SPEI is 0.4 lower for hazardous than for non-hazardous ecosystem behaviour. In northern Germany, on the contrary, the site is not vulnerable to drought because the SPEI expectation values imply wetter conditions in the hazard case than in the non-hazard case.
At the pan-European scale, ecosystem vulnerability to drought is calculated in the Mediterranean and temperate region, whereas Scandinavian ecosystems are vulnerable under conditions without water shortages. These first model- based applications indicate the conceptual advantages of the proposed method by focusing on the identification of critical weather conditions for which we observe hazardous ecosystem behaviour in the analysed data set. Application of the method to empirical time series and to future climate would be important next steps to test the approach.
This study investigates the spatial and temporal distributions of 14 key arboreal taxa and their driving forces during the last 22,000 calendar years before ad 1950 (kyr BP) using a taxonomically harmonized and temporally standardized fossil pollen dataset with a 500-year resolution from the eastern part of continental Asia. Logistic regression was used to estimate pollen abundance thresholds for vegetation occurrence (presence or dominance), based on modern pollen data and present ranges of 14 taxa in China. Our investigation reveals marked changes in spatial and temporal distributions of the major arboreal taxa. The thermophilous (Castanea, Castanopsis, Cyclobalanopsis, Fagus, Pterocarya) and eurythermal (Juglans, Quercus, Tilia, Ulmus) broadleaved tree taxa were restricted to the current tropical or subtropical areas of China during the Last Glacial Maximum (LGM) and spread northward since c. 14.5 kyr BP. Betula and conifer taxa (Abies, Picea, Pinus), in contrast, retained a wider distribution during the LGM and showed no distinct expansion direction during the Late Glacial. Since the late mid-Holocene, the abundance but not the spatial extent of most trees decreased. The changes in spatial and temporal distributions for the 14 taxa are a reflection of climate changes, in particular monsoonal moisture, and, in the late Holocene, human impact. The post-LGM expansion patterns in eastern continental China seem to be different from those reported for Europe and North America, for example, the westward spread for eurythermal broadleaved taxa.
This study examines the course and driving forces of recent vegetation change in the Mongolian steppe. A sediment core covering the last 55years from a small closed-basin lake in central Mongolia was analyzed for its multi-proxy record at annual resolution. Pollen analysis shows that highest abundances of planted Poaceae and highest vegetation diversity occurred during 1977-1992, reflecting agricultural development in the lake area. A decrease in diversity and an increase in Artemisia abundance after 1992 indicate enhanced vegetation degradation in recent times, most probably because of overgrazing and farmland abandonment. Human impact is the main factor for the vegetation degradation within the past decades as revealed by a series of redundancy analyses, while climate change and soil erosion play subordinate roles. High Pediastrum (a green algae) influx, high atomic total organic carbon/total nitrogen (TOC/TN) ratios, abundant coarse detrital grains, and the decrease of C-13(org) and N-15 since about 1977 but particularly after 1992 indicate that abundant terrestrial organic matter and nutrients were transported into the lake and caused lake eutrophication, presumably because of intensified land use. Thus, we infer that the transition to a market economy in Mongolia since the early 1990s not only caused dramatic vegetation degradation but also affected the lake ecosystem through anthropogenic changes in the catchment area.
Two of a kind?
(2014)
School attacks are attracting increasing attention in aggression research. Recent systematic analyses provided new insights into offense and offender characteristics. Less is known about attacks in institutes of higher education (e.g., universities). It is therefore questionable whether the term “school attack” should be limited to institutions of general education or could be extended to institutions of higher education. Scientific literature is divided in distinguishing or unifying these two groups and reports similarities as well as differences. We researched 232 school attacks and 45 attacks in institutes of higher education throughout the world and conducted systematic comparisons between the two groups. The analyses yielded differences in offender (e.g., age, migration background) and offense characteristics (e.g., weapons, suicide rates), and some similarities (e.g., gender). Most differences can apparently be accounted for by offenders’ age and situational influences. We discuss the implications of our findings for future research and the development of preventative measures.
Leaking comprises observable behavior or statements that signal intentions of committing a violent offense and is considered an important warning sign for school shootings. School staff who are confronted with leaking have to assess its seriousness and react appropriately - a difficult task, because knowledge about leaking is sparse. The present study, therefore, examined how frequently leaking occurs in schools and how teachers identify leaking and respond to it. To achieve this aim, we informed teachers from eight schools in Germany about the definition of leaking and other warning signs and risk factors for school shootings in a one-hour information session. Teachers were then asked to report cases of leaking over a six- to nine-month period and to answer a questionnaire on leaking and its treatment after the information session and six to nine months later. Our results suggest that leaking is a relevant problem in German schools. Teachers mostly rated the information session positively and benefited in several aspects (e.g. reported more perceived courses of action or improved knowledge about leaking), but also expressed a constant need for support. Our findings highlight teachers' needs for further support and training and may be used in the planning of prevention measures for school shootings.
Although politicization is a perennial research topic in public administration to investigate relationships between ministers and civil servants, the concept still lacks clarification. This article contributes to this literature by systematically identifying different conceptualizations of politicization and suggests a typology including three politicization mechanisms to strengthen the political responsiveness of the ministerial bureaucracy: formal, functional and administrative politicization. The typology is empirically validated through a comparative case analysis of politicization mechanisms in Germany, Belgium, the UK and Denmark. The empirical analysis further refines the general idea of Western democracies becoming ‘simply’ more politicized, by illustrating how some politicization mechanisms do not continue to increase, but stabilize – at least for the time being.
Background Transcatheter aortic-valve implantation (TAVI) is an established alternative therapy in patients with severe aortic stenosis and a high surgical risk. Despite a rapid growth in its use, very few data exist about the efficacy of cardiac rehabilitation (CR) in these patients. We assessed the hypothesis that patients after TAVI benefit from CR, compared to patients after surgical aortic-valve replacement (sAVR).
Methods From September 2009 to August 2011, 442 consecutive patients after TAVI (n=76) or sAVR (n=366) were referred to a 3-week CR. Data regarding patient characteristics as well as changes of functional (6-min walk test. 6-MWT), bicycle exercise test), and emotional status (Hospital Anxiety and Depression Scale) were retrospectively evaluated and compared between groups after propensity score adjustment.
Results Patients after TAVI were significantly older (p<0.001), more female (p<0.001), and had more often coronary artery disease (p=0.027), renal failure (p=0.012) and a pacemaker (p=0.032). During CR, distance in 6-MWT (both groups p0.001) and exercise capacity (sAVR p0.001, TAVI p0.05) significantly increased in both groups. Only patients after sAVR demonstrated a significant reduction in anxiety and depression (p0.001). After propensity scores adjustment, changes were not significantly different between sAVR and TAVI, with the exception of 6-MWT (p=0.004).
Conclusions Patients after TAVI benefit from cardiac rehabilitation despite their older age and comorbidities. CR is a helpful tool to maintain independency for daily life activities and participation in socio-cultural life.
Background: Chronic kidney disease (CKD) is a frequent comorbidity among elderly patients and those with cardiovascular disease. CKD carries prognostic relevance. We aimed to describe patient characteristics, risk factor management and control status of patients in cardiac rehabilitation (CR), differentiated by presence or absence of CKD.
Design and methods: Data from 92,071 inpatients with adequate information to calculate glomerular filtration rate (GFR) based on the Cockcroft-Gault formula were analyzed at the beginning and the end of a 3-week CR stay. CKD was defined as estimated GFR <60 ml/min/1.73 m(2).
Results: Compared with non-CKD patients, CKD patients were significantly older (72.0 versus 58.0 years) and more often had diabetes mellitus, arterial hypertension, and atherothrombotic manifestations (previous stroke, peripheral arterial disease), but fewer were current or previous smokers had a CHD family history. Exercise capacity was much lower in CKD (59 vs. 92Watts). Fewer patients with CKD were treated with percutaneous coronary intervention (PCI), but more had coronary artery bypass graft (CABG) surgery. Patients with CKD compared with non-CKD less frequently received statins, acetylsalicylic acid (ASA), clopidogrel, beta blockers, and angiotensin converting enzyme (ACE) inhibitors, and more frequently received angiotensin receptor blockers, insulin and oral anticoagulants. In CKD, mean low density lipoprotein cholesterol (LDL-C), total cholesterol, and high density lipoprotein cholesterol (HDL-C) were slightly higher at baseline, while triglycerides were substantially lower. This lipid pattern did not change at the discharge visit, but overall control rates for all described parameters (with the exception of HDL-C) were improved substantially. At discharge, systolic blood pressure (BP) was higher in CKD (124 versus 121 mmHg) and diastolic BP was lower (72 versus 74 mmHg). At discharge, 68.7% of CKD versus 71.9% of non-CKD patients had LDL-C <100 mg/dl. Physical fitness on exercise testing improved substantially in both groups. When the Modification of Diet in Renal Disease (MDRD) formula was used for CKD classification, there was no clinically relevant change in these results.
Conclusion: Within a short period of 3-4 weeks, CR led to substantial improvements in key risk factors such as lipid profile, blood pressure, and physical fitness for all patients, even if CKD was present.
Background: Knowing and, if necessary, altering competitive athletes' real attitudes towards the use of banned performance-enhancing substances is an important goal of worldwide doping prevention efforts. However athletes will not always be willing to reporting their real opinions. Reaction time-based attitude tests help conceal the ultimate goal of measurement from the participant and impede strategic answering. This study investigated how well a reaction time-based attitude test discriminated between athletes who were doping and those who were not. We investigated whether athletes whose urine samples were positive for at least one banned substance (dopers) evaluated doping more favorably than clean athletes (non-dopers).
Methods: We approached a group of 61 male competitive bodybuilders and collected urine samples for biochemical testing. The pictorial doping Brief Implicit Association Test (BIAT) was used for attitude measurement. This test quantifies the difference in response latencies (in milliseconds) to stimuli representing related concepts (i.e. doping-dislike/like-[health food]).
Results: Prohibited substances were found in 43% of all tested urine samples. Dopers had more lenient attitudes to doping than non-dopers (Hedges's g = -0.76). D-scores greater than -0.57 (CI95 = -0.72 to -0.46) might be indicative of a rather lenient attitude to doping. In urine samples evidence of administration of combinations of substances, complementary administration of substances to treat side effects and use of stimulants to promote loss of body fat was common.
Conclusion: This study demonstrates that athletes' attitudes to doping can be assessed indirectly with a reaction time-based test, and that their attitudes are related to their behavior. Although bodybuilders may be more willing to reveal their attitude to doping than other athletes, these results still provide evidence that the pictorial doping BIAT may be useful in athletes from other sports, perhaps as a complementary measure in evaluations of the effectiveness of doping prevention interventions.
Background
The Amazon molly, Poecilia formosa (Teleostei: Poeciliinae) is an unisexual, all-female species. It evolved through the hybridisation of two closely related sexual species and exhibits clonal reproduction by sperm dependent parthenogenesis (or gynogenesis) where the sperm of a parental species is only used to activate embryogenesis of the apomictic, diploid eggs but does not contribute genetic material to the offspring.
Here we provide and describe the first de novo assembled transcriptome of the Amazon molly in comparison with its maternal ancestor, the Atlantic molly Poecilia mexicana. The transcriptome data were produced through sequencing of single end libraries (100 bp) with the Illumina sequencing technique.
Results
83,504,382 reads for the Amazon molly and 81,625,840 for the Atlantic molly were assembled into 127,283 and 78,961 contigs for the Amazon molly and the Atlantic molly, respectively. 63% resp. 57% of the contigs could be annotated with gene ontology terms after sequence similarity comparisons. Furthermore, we were able to identify genes normally involved in reproduction and especially in meiosis also in the transcriptome dataset of the apomictic reproducing Amazon molly.
Conclusions
We assembled and annotated the transcriptome of a non-model organism, the Amazon molly, without a reference genome (de novo). The obtained dataset is a fundamental resource for future research in functional and expression analysis. Also, the presence of 30 meiosis-specific genes within a species where no meiosis is known to take place is remarkable and raises new questions for future research.
Background: Cross-sectional studies detected associations between physical fitness, living area, and sports participation in children. Yet, their scientific value is limited because the identification of cause-and-effect relationships is not possible. In a longitudinal approach, we examined the effects of living area and sports club participation on physical fitness development in primary school children from classes 3 to 6.
Methods: One-hundred and seventy-two children (age: 9-12 years; sex: 69 girls, 103 boys) were tested for their physical fitness (i.e., endurance [9-min run], speed [50-m sprint], lower- [triple hop] and upper-extremity muscle strength [1-kg ball push], flexibility [stand-and-reach], and coordination [star coordination run]). Living area (i.e., urban or rural) and sports club participation were assessed using parent questionnaire.
Results: Over the 4 year study period, urban compared to rural children showed significantly better performance development for upper- (p = 0.009, ES = 0.16) and lower-extremity strength (p < 0.001, ES = 0.22). Further, significantly better performance development were found for endurance (p = 0.08, ES = 0.19) and lower-extremity strength (p = 0.024, ES = 0.23) for children continuously participating in sports clubs compared to their non-participating peers.
Conclusions: Our findings suggest that sport club programs with appealing arrangements appear to represent a good means to promote physical fitness in children living in rural areas.
Background: Doping attitude is a key variable in predicting athletes' intention to use forbidden performance enhancing drugs. Indirect reaction-time based attitude tests, such as the implicit association test, conceal the ultimate goal of measurement from the participant better than questionnaires. Indirect tests are especially useful when socially sensitive constructs such as attitudes towards doping need to be described. The present study serves the development and validation of a novel picture-based brief implicit association test (BIAT) for testing athletes' attitudes towards doping in sport. It shall provide the basis for a transnationally compatible research instrument able to harmonize anti-doping research efforts.
Method: Following a known-group differences validation strategy, the doping attitudes of 43 athletes from bodybuilding (representative for a highly doping prone sport) and handball (as a contrast group) were compared using the picture-based doping-BIAT. The Performance Enhancement Attitude Scale (PEAS) was employed as a corresponding direct measure in order to additionally validate the results.
Results: As expected, in the group of bodybuilders, indirectly measured doping attitudes as tested with the picture-based doping-BIAT were significantly less negative (eta(2) = .11). The doping-BIAT and PEAS scores correlated significantly at r = .50 for bodybuilders, and not significantly at r = .36 for handball players. There was a low error rate (7%) and a satisfactory internal consistency (r(dagger dagger) = .66) for the picture-based doping-BIAT.
Conclusions: The picture-based doping-BIAT constitutes a psychometrically tested method, ready to be adopted by the international research community. The test can be administered via the internet. All test material is available "open source". The test might be implemented, for example, as a new effect-measure in the evaluation of prevention programs.
The nature of the links between speech production and perception has been the subject of longstanding debate. The present study investigated the articulatory parameter of tongue height and the acoustic F1–F0 difference for the phonological distinction of vowel height in American English front vowels. Multiple repetitions of /i, ɪ, e, ɛ, æ/ in [(h)Vd] sequences were recorded in seven adult speakers. Articulatory (ultrasound) and acoustic data were collected simultaneously to provide a direct comparison of variability in vowel production in both domains. Results showed idiosyncratic patterns of articulation for contrasting the three front vowel pairs /i-ɪ/, /e-ɛ/, and /ɛ-æ/ across subjects, with the degree of variability in vowel articulation comparable to that observed in the acoustics for all seven participants. However, contrary to what was expected, some speakers showed reversals for tongue height for /ɪ/-/e/ that were also reflected in acoustics, with F1 higher for /ɪ/ than for /e/. The data suggest the phonological distinction of height is conveyed via speaker-specific articulatory-acoustic patterns that do not strictly match features descriptions. However, the acoustic signal is faithful to the articulatory configuration that generated it, carrying the crucial information for perceptual contrast.
Previous studies suggest that there are special timing relations in syllable onsets. The consonants are assumed to be timed, on the one hand, with the vocalic nucleus and, on the other hand, with each other. These competing timing relations result in the C-center effect. However, the C-center effect has not consistently been found in languages with complex onsets. Moreover, it has occasionally been found in languages disallowing complex onsets. The present study investigates onset timing in German while discussing alternative explanations (not related to bonding) for the timing patterns observed. Six German speakers were recorded via Electromagnetic Articulography. The corpus contained items with four clusters (/sk/, /kv/, /gl/, and /pl/). The clusters occur in word-initial position, word-medial position, and across a word boundary preceding different vowels. The results suggest that segmental properties (i.e., oral-laryngeal coordination, coarticulatory resistance) determine the observed timing patterns, and specifically the absence or presence of the C-center effect.
Rezensiertes Werk:
George, Rosemary Marangoly, Indian English and the Fiction of National Literature - Cambridge: Cambridge University Press, 2013. - Hb. viii, 285 pp. - (Zeitschrift für Anglistik und Amerikanistik ; 62(4)) ISBN 978-1-107-04000-7.
In the Posthomerica references to an omnipotent fate or to the power of the gods are strikingly frequent. Modern scholarship has often treated this as Stoic. Closer reading reveals that Quintus is, on the one hand, following the Homeric concept of double motivation, according to which humans can be motivated by a deity only to an act that conforms to their character and for which they are responsible. On the other hand, Quintus gives these statements on responsibility to characters who are trying to excuse their own acts to themselves and, particularly, to others, i.e. they are motivated contextually. It would be non-Stoic to excuse oneself for a bad deed by reference to an almighty fate. It seems that Quintus, by presenting this tension, wanted the reader to reconsider and reflect
on the different concepts.
Moderne Kraftfahrzeuge verfügen über eine Vielzahl an Sensoren, welche für einen reibungslosen technischen Betrieb benötigt werden. Hierzu zählen neben fahrzeugspezifischen Sensoren (wie z.B. Motordrehzahl und Fahrzeuggeschwindigkeit) auch umweltspezifische Sensoren (wie z.B. Luftdruck und Umgebungstemperatur). Durch die zunehmende technische Vernetzung wird es möglich, diese Daten der Kraftfahrzeugelektronik aus dem Fahrzeug heraus für die verschiedensten Zwecke zu verwenden.
Die vorliegende Arbeit soll einen Beitrag dazu leisten, diese neue Art an massenhaften Daten im Sinne des Konzepts der „Extended Floating Car Data“ (XFCD) als Geoinformationen nutzbar zu machen und diese für raumzeitliche Visualisierungen (zur visuellen Analyse) anwenden zu können. In diesem Zusammenhang wird speziell die Perspektive des Umwelt- und Verkehrsmonitoring betrachtet, wobei die Anforderungen und Potentiale mit Hilfe von Experteninterviews untersucht werden. Es stellt sich die Frage, welche Daten durch die Kraftfahrzeugelektronik geliefert und wie diese möglichst automatisiert erfasst, verarbeitet, visualisiert und öffentlich bereitgestellt werden können. Neben theoretischen und technischen Grundlagen zur Datenerfassung und -nutzung liegt der Fokus auf den Methoden der kartographischen Visualisierung. Dabei soll der Frage nachgegangenen werden, ob eine technische Implementierung ausschließlich unter Verwendung von Open Source Software möglich ist. Das Ziel der Arbeit bildet ein zweigliedriger Ansatz, welcher zum einen die Visualisierung für ein exemplarisch gewähltes Anwendungsszenario und zum anderen die prototypische Implementierung von der Datenerfassung im Fahrzeug unter Verwendung der gesetzlich vorgeschriebenen „On Board Diagnose“-Schnittstelle und einem Smartphone-gestützten Ablauf bis zur webbasierten Visualisierung umfasst.
Downscaling of microfluidic cell culture and detection devices for electrochemical monitoring has mostly focused on miniaturization of the microfluidic chips which are often designed for specific applications and therefore lack functional flexibility. We present a compact microfluidic cell culture and electrochemical analysis platform with in-built fluid handling and detection, enabling complete cell based assays comprising on-line electrode cleaning, sterilization, surface functionalization, cell seeding, cultivation and electrochemical real-time monitoring of cellular dynamics. To demonstrate the versatility and multifunctionality of the platform, we explored amperometric monitoring of intracellular redox activity in yeast (Saccharomyces cerevisiae) and detection of exocytotically released dopamine from rat pheochromocytoma cells (PC12). Electrochemical impedance spectroscopy was used in both applications for monitoring cell sedimentation and adhesion as well as proliferation in the case of PC12 cells. The influence of flow rate on the signal amplitude in the detection of redox metabolism as well as the effect of mechanical stimulation on dopamine release were demonstrated using the programmable fluid handling capability. The here presented platform is aimed at applications utilizing cell based assays, ranging from e.g. monitoring of drug effects in pharmacological studies, characterization of neural stem cell differentiation, and screening of genetically modified microorganisms to environmental monitoring.
Hemolysis, the rupturing of red blood cells, can result from numerous medical conditions (in vivo) or occur after collecting blood specimen or extracting plasma and serum out of whole blood (in vitro). In clinical laboratory practice, hemolysis can be a serious problem due to its potential to bias detection of various analytes or biomarkers. Here we present the first ‘‘mix-and-measure’’ method to assess the degree of hemolysis in biosamples using luminescence spectroscopy. Luminescent terbium complexes (LTC) were studied in the presence of free hemoglobin (Hb) as indicators for hemolysis in TRIS-buffer, and in fresh human plasma with absorption, excitation and emission measurements. Our findings indicate dynamic as well as resonance energy transfer (FRET) between the LTC and the porphyrin ligand of hemoglobin. This transfer leads to a decrease in luminescence intensity and decay time even at nanomolar hemoglobin concentrations either in buffer or plasma. Luminescent terbium complexes are very sensitive to free hemoglobin in buffer and blood plasma. Due to the instant change in luminescence properties of the LTC in presence of Hb it is possible to access the concentration of hemoglobin via spectroscopic methods without incubation time or further treatment of the sample thus enabling a rapid and sensitive detection of hemolysis in clinical diagnostics.
Surface modification with thermoresponsive polymer brushes for a switchable electrochemical sensor
(2014)
Elaboration of switchable surfaces represents an interesting way for the development of a new generation of electrochemical sensors. In this paper, a method for growing thermoresponsive polymer brushes from a gold surface pre-modified with polyethyleneimine (PEI), subsequent layer-by-layer polyelectrolyte assembly and adsorption of a charged macroinitiator is described. We propose an easy method for monitoring the coil-to-globule phase transition of the polymer brush using an electrochemical quartz crystal microbalance with dissipation (E-QCM-D). The surface of these polymer modified electrodes shows reversible switching from the swollen to the collapsed state with temperature. As demonstrated from E-QCM-D measurements using an original signal processing method, the switch is operating in three reversible steps related to different interfacial viscosities. Moreover, it is shown that the one electron oxidation of ferrocene carboxylic acid is dramatically affected by the change from the swollen to the collapsed state of the polymer brush, showing a spectacular 86% decrease of the charge transfer resistance between the two states.
Two-photon polymerization of hydrogels – versatile solutions to fabricate well-defined 3D structures
(2014)
Hydrogels are cross-linked water-containing polymer networks that are formed by physical, ionic or covalent interactions. In recent years, they have attracted significant attention because of their unique physical properties, which make them promising materials for numerous applications in food and cosmetic processing, as well as in drug delivery and tissue engineering. Hydrogels are highly water-swellable materials, which can considerably increase in volume without losing cohesion, are biocompatible and possess excellent tissue-like physical properties, which can mimic in vivo conditions. When combined with highly precise manufacturing technologies, such as two-photon polymerization (2PP), well-defined three-dimensional structures can be obtained. These structures can become scaffolds for selective cell-entrapping, cell/drug delivery, sensing and prosthetic implants in regenerative medicine. 2PP has been distinguished from other rapid prototyping methods because it is a non-invasive and efficient approach for hydrogel cross-linking. This review discusses the 2PP-based fabrication of 3D hydrogel structures and their potential applications in biotechnology. A brief overview regarding the 2PP methodology and hydrogel properties relevant to biomedical applications is given together with a review of the most important recent achievements in the field.
Hemocompatible materials are needed for internal and extracorporeal biomedical applications, which should be realizable by reducing protein and thrombocyte adhesion to such materials. Polyethers have been demonstrated to be highly efficient in this respect on smooth surfaces. Here, we investigate the grafting of oligo- and polyglycerols to rough poly(ether imide) membranes as a polymer relevant to biomedical applications and show the reduction of protein and thrombocyte adhesion as well as thrombocyte activation. It could be demonstrated that, by performing surface grafting with oligo- and polyglycerols of relatively high polydispersity (>1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials.
Polyglycolide (PGA) is a biodegradable polymer with multiple applications in the medical sector. Here the synthesis of high molecular weight polyglycolide by ring-opening polymerization of diglycolide is reported. For the first time stabilizer free supercritical carbon dioxide (scCO2) was used as a reaction medium. scCO2 allowed for a reduction in reaction temperature compared to conventional processes. Together with the lowering of monomer concentration and consequently reduced heat generation compared to bulk reactions thermal decomposition of the product occurring already during polymerization is strongly reduced. The reaction temperatures and pressures were varied between 120 and 150 °C and 145 to 1400 bar. Tin(II) ethyl hexanoate and 1-dodecanol were used as catalyst and initiator, respectively. The highest number average molecular weight of 31 200 g mol−1 was obtained in 5 hours from polymerization at 120 °C and 530 bar. In all cases the products were obtained as a dry white powder. Remarkably, independent of molecular weight the melting temperatures were always at (219 ± 2) °C.
The large-scale green synthesis of graphene-type two-dimensional materials is still challenging. Herein, we describe the ionothermal synthesis of carbon-based composites from fructose in the iron-containing ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III), [Bmim][FeCl4] serving as solvent, catalyst, and template for product formation. The resulting composites consist of oligo-layer graphite nanoflakes and iron carbide particles. The mesoporosity, strong magnetic moment, and high specific surface area of the composites make them attractive for water purification with facile magnetic separation. Moreover, Fe3Cfree graphite can be obtained via acid etching, providing access to fairly large amounts of graphite material. The current approach is versatile and scalable, and thus opens the door to ionothermal synthesis towards the larger-scale synthesis of materials that are, although not made via a sustainable process, useful for water treatment such as the removal of organic molecules.
Catalytic bio–chemo and bio–bio tandem oxidation reactions for amide and carboxylic acid synthesis
(2014)
A catalytic toolbox for three different water-based one-pot cascades to convert aryl alcohols to amides and acids and cyclic amines to lactams, involving combination of oxidative enzymes (monoamine oxidase, xanthine dehydrogenase, galactose oxidase and laccase) and chemical oxidants (TBHP or CuI(cat)/H2O2) at mild temperatures, is presented. Mutually compatible conditions were found to afford products in good to excellent yields.
Zinc deficiency has a fundamental influence on the immune defense, with multiple effects on different immune cells, resulting in a major impairment of human health. Monocytes and macrophages are among the immune cells that are most fundamentally affected by zinc, but the impact of zinc on these cells is still far from being completely understood. Therefore, this study investigates the influence of zinc deficiency on monocytes of healthy human donors. Peripheral blood mononuclear cells, which include monocytes, were cultured under zinc deficient conditions for 3 days. This was achieved by two different methods: by application of the membrane permeable chelator N,N,N0´,N0´-tetrakis-(2-pyridylmethyl)ethylenediamine (TPEN) or by removal of zinc from the culture medium using a CHELEX 100 resin. Subsequently, monocyte functions were analyzed in response to Escherichia coli, Staphylococcus aureus, and Streptococcus pneumoniae. Zinc depletion had differential effects. On the one hand, elimination of bacterial pathogens by phagocytosis and oxidative burst was elevated. On the other hand, the production of the inflammatory cytokines tumor necrosis factor (TNF)-a and interleukin (IL)-6 was reduced. This suggests that monocytes shift from intercellular communication to basic innate defensive functions in response to zinc deficiency. These results were obtained regardless of the method by which zinc deficiency was achieved. However, CHELEX-treated medium strongly augmented cytokine production, independently from its capability for zinc removal. This side-effect severely limits the use of CHELEX for investigating the effects of zinc deficiency on innate immunity.
The synthesis of two novel types of π-expanded coumarins has been developed. Modified Knoevenagel bis-condensation afforded 3,9-dioxa-perylene-2,8-diones. Subsequent oxidative aromatic coupling or light driven electrocyclization reaction led to dibenzo-1,7-dioxacoronene-2,8-dione. Unparalleled synthetic simplicity, straightforward purification and superb optical properties have the potential to bring these perylene and coronene analogs towards various applications.
Photoinduced excitation energy transfer and accompanying charge separation are elucidated for a supramolecular system of a single fullerene covalently linked to six pyropheophorbide-a dye molecules. Molecular dynamics simulations are performed to gain an atomistic picture of the architecture and the surrounding solvent. Excitation energy transfer among the dye molecules and electron transfer from the excited dyes to the fullerene are described by a mixed quantum–classical version of the Förster rate and the semiclassical Marcus rate, respectively. The mean characteristic time of energy redistribution lies in the range of 10 ps, while electron transfer proceeds within 150 ps. In between, on a 20 to 50 ps time-scale, conformational changes take place in the system. This temporal hierarchy of processes guarantees efficient charge separation, if the structure is exposed to a solvent. The fast energy transfer can adopt the dye excitation to the actual conformation. In this sense, the probability to achieve charge separation is large enough since any dominance of unfavorable conformations that exhibit a large dye–fullerene distance is circumvented. And the slow electron transfer may realize an averaging with respect to different conformations. To confirm the reliability of our computations, ensemble measurements on the charge separation dynamics are simulated and a very good agreement with the experimental data is obtained.
Based on extensive Monte Carlo simulations and analytical considerations we study the electrostatically driven adsorption of flexible polyelectrolyte chains onto charged Janus nanospheres. These net-neutral colloids are composed of two equally but oppositely charged hemispheres. The critical binding conditions for polyelectrolyte chains are analysed as function of the radius of the Janus particle and its surface charge density, as well as the salt concentration in the ambient solution. Specifically for the adsorption of finite-length polyelectrolyte chains onto Janus nanoparticles, we demonstrate that the critical adsorption conditions drastically differ when the size of the Janus particle or the screening length of the electrolyte are varied. We compare the scaling laws obtained for the adsorption–desorption threshold to the known results for uniformly charged spherical particles, observing significant disparities. We also contrast the changes to the polyelectrolyte chain conformations close to the surface of the Janus nanoparticles as compared to those for simple spherical particles. Finally, we discuss experimentally relevant physico-chemical systems for which our simulations results may become important. In particular, we observe similar trends with polyelectrolyte complexation with oppositely but heterogeneously charged proteins.
Formation of a Eu(III) borate solid species from a weak Eu(III) borate complex in aqueous solution
(2014)
In the presence of polyborates (detected by 11B-NMR) the formation of a weak Eu(III) borate complex (lg β11 ∼ 2, estimated) was observed by time-resolved laser-induced fluorescence spectroscopy (TRLFS). This complex is a precursor for the formation of a solid Eu(III) borate species. The formation of this solid in solution was investigated by TRLFS as a function of the total boron concentration: the lower the total boron concentration, the slower is the solid formation. The solid Eu(III) borate was characterized by IR spectroscopy, powder XRD and solid-state TRLFS. The determination of the europium to boron ratio portends the existence of pentaborate units in the amorphous solid.
A feasible approach to construct multilayer films of sulfonated polyanilines – PMSA1 and PABMSA1 – containing different ratios of aniline, 2-methoxyaniline-5-sulfonic acid (MAS) and 3-aminobenzoic acid (AB), with the entrapped redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) on Au and ITO electrode surfaces, is described. The formation of layers has been followed and confirmed by electrochemical impedance spectroscopy (EIS), which demonstrates that the multilayer assembly can be achieved in a progressive and uniform manner. The gold and ITO electrodes subsequently modified with PMSA1:PQQ-GDH and PABMSA1 films are studied by cyclic voltammetry (CV) and UV-Vis spectroscopy which show a significant direct bioelectrocatalytical response to the oxidation of the substrate glucose without any additional mediator. This response correlates linearly with the number of deposited layers. Furthermore, the constructed polymer/enzyme multilayer system exhibits a rather good long-term stability, since the catalytic current response is maintained for more than 60% of the initial value even after two weeks of storage. This verifies that a productive interaction of the enzyme embedded in the film of substituted polyaniline can be used as a basis for the construction of bioelectronic units, which are useful as indicators for processes liberating glucose and allowing optical and electrochemical transduction.
As an engineering material derived from renewable resources, wood possesses excellent mechanical properties in view of its light weight but also has some disadvantages such as low dimensional stability upon moisture changes and low durability against biological attack. Polymerization of hydrophobic monomers in the cell wall is one of the potential approaches to improve the dimensional stability of wood. A major challenge is to insert hydrophobic monomers into the hydrophilic environment of the cell walls, without increasing the bulk density of the material due to lumen filling. Here, we report on an innovative and simple method to insert styrene monomers into tosylated cell walls (i.e. –OH groups from natural wood polymers are reacted with tosyl chloride) and carry out free radical polymerization under relatively mild conditions, generating low wood weight gains. In-depth SEM and confocal Raman microscopy analysis are applied to reveal the distribution of the polystyrene in the cell walls and the lumen. The embedding of polystyrene in wood results in reduced water uptake by the wood cell walls, a significant increase in dimensional stability, as well as slightly improved mechanical properties measured by nanoindentation.
Herein, we report the chain-growth tin-free room temperature polymerization method to synthesize n-type perylene diimide-dithiophene-based conjugated polymers (PPDIT2s) suitable for solar cell and transistor applications. The palladium/electron-rich tri-tert-butylphosphine catalyst is effective to enable the chain-growth polymerization of anion-radical monomer Br-TPDIT-Br/Zn to PPDIT2 with a molecular weight up to Mw ≈ 50 kg mol−1 and moderate polydispersity. This is the second example of the polymerization of unusual anion-radical aromatic complexes formed in a reaction of active Zn and electron-deficient diimide-based aryl halides. As such, the discovered polymerization method is not a specific reactivity feature of the naphthalene-diimide derivatives but is rather a general polymerization tool. This is an important finding, given the significantly higher maximum external quantum efficiency that can be reached with PDI-based copolymers (32–45%) in all-polymer solar cells compared to NDI-based materials (15–30%). Our studies revealed that PPDIT2 synthesized by the new method and the previously published polymer prepared by step-growth Stille polycondensation show similar electron mobility and all-polymer solar cell performance. At the same time, the polymerization reported herein has several technological advantages as it proceeds relatively fast at room temperature and does not involve toxic tin-based compounds. Because several chain-growth polymerization reactions are well-suited for the preparation of well-defined multi-functional polymer architectures, the next target is to explore the utility of the discovered polymerization in the synthesis of end-functionalized polymers and block copolymers. Such materials would be helpful to improve the nanoscale morphology of polymer blends in all-polymer solar cells.
Materials derived from renewable resources are highly desirable in view of more sustainable manufacturing. Among the available natural materials, wood is one of the key candidates, because of its excellent mechanical properties. However, wood and wood-based materials in engineering applications suffer from various restraints, such as dimensional instability upon humidity changes. Several wood modification treatments increase water repellence, but the insertion of hydrophobic polymers can result in a composite material which cannot be considered as renewable anymore. In this study, we report on the grafting of the fully biodegradable poly(ε-caprolactone) (PCL) inside the wood cell walls by Sn(Oct)2 catalysed ring-opening polymerization (ROP). The presence of polyester chains within the wood cell wall structure is monitored by confocal Raman imaging and spectroscopy as well as scanning electron microscopy. Physical tests reveal that the modified wood is more hydrophobic due to the bulking of the cell wall structure with the polyester chains, which results in a novel fully biodegradable wood material with improved dimensional stability.
A new functional luminescent lanthanide complex (LLC) has been synthesized with terbium as a central lanthanide ion and biotin as a functional moiety. Unlike in typical lanthanide complexes assembled via carboxylic moieties, in the presented complex, four phosphate groups are chelating the central lanthanide ion. This special chemical assembly enhances the complex stability in phosphate buffers conventionally used in biochemistry. The complex synthesis strategy and photophysical properties are described as well as the performance in time-resolved Förster Resonance Energy Transfer (FRET) assays. In those assays, this biotin-LLC transferred energy either to acceptor organic dyes (Cy5 or AF680) labelled on streptavidin or to quantum dots (QD655 or QD705) surface-functionalised with streptavidins. The permanent spatial donor–acceptor proximity is assured through strong and stable biotin–streptavidin binding. The energy transfer is evidenced from the quenching observed in donor emission and from a decrease in donor luminescence decay, both associated with simultaneous increase in acceptor intensity and in the decay time. The dye-based assays are realised in TRIS and in PBS, whereas QD-based systems are studied in borate buffer. The delayed emission analysis allows for quantifying the recognition process and for auto-fluorescence-free detection, which is particularly relevant for application in bioanalysis. In accordance with Förster theory, Förster-radii (R0) were found to be around 60 Å for organic dyes and around 105 Å for QDs. The FRET efficiency (η) reached 80% and 25% for dye and QD acceptors, respectively. Physical donor–acceptor distances (r) have been determined in the range 45–60 Å for organic dye acceptors, while for acceptor QDs between 120 Å and 145 Å. This newly synthesised biotin-LLC extends the class of highly sensitive analytical tools to be applied in the bioanalytical methods such as time-resolved fluoroimmunoassays (TR-FIA), luminescent imaging and biosensing.
Dieser Artikel adressiert zwei bisher nur wenig untersuchte Aspekte der Führungsforschung: Führungsverhalten im öffentlichen Sektor und Faktoren die Führungsverhalten beeinflussen. Mittels einer Fallstudie in der Bundesagentur für Arbeit werden explorativ Hypothesen über Einflussfaktoren des Führungsverhaltens aufgestellt. Die Studie kommt zu der Erkenntnis, dass eine oftmals angenommene Führungslücke im öffentlichen Sektor nicht bestätigt werden kann. Für das ausgeprägte Führungsverhalten, das in der Fallstudie beobachtet wurde, wird als Determinante die besondere Ausgestaltung des Managementsystems der Bundesagentur für Arbeit verantwortlich gemacht. Dazu gehört unter anderem das Performance Management System sowie die Führungskräfteauswahl und -entwicklung. Die Arbeit schließt mit Empfehlungen für weitere Forschungsansätze auf dem Gebiet der Führungsforschung im öffentlichen Sektor.
This essay approaches T. S. Eliot’s Four Quartets (1935–1942) from the perspectives of Eve Kosofsky Sedgwick’s critical practice of reparative reading and of Paul Ricoeur’s poststructuralist hermeneutics. It demonstrates that Sedgwick’s and Ricoeur’s approaches can be productively combined to investigate hermeneutic processes in which the textual energy of a dissemination of meaning is redirected by a reparative or integrative impulse. In Four Quartets, this impetus induces the creation of semantic innovation through a violation of semantic pertinence, that is, through novel, tensional and provisional connections between formerly separate textual elements and semantic units.
The system of German capitalisation seems to be based on dissimilar levels of linguistic description, i. e. semantics, morphology, and syntax. This leads to several competing scientific models as well as a large range of different rules which appear to be widely autonomous and incompatible with each other. This paper opens an integrative view on the topic by focussing on a pragmatic perspective, which is capable not only on integrating all major application areas of German capitalisation but also of motivating them. Based on theDiscourse Representation Theory (DRT) the text pragmatic model can add a functional perspective to established theories by making similar predictions on capitalisation but additionally specifying communicative reasons for them. Therefore it claims explanatory adequacy from the functional perspective.
Werner Mittenzwei’s article of 1967, the title of which coined the term “Brecht-Lukács-Debatte”, is widely considered as a milestone in the development of East German literary criticism towards an “emancipation” from party politics. By placing Mittenzwei’s contribution in the wider context of discussions about the literature of the GDR, within the SED and the writers’ union as well as at international conferences, this article attempts to trace the emergence of “Umfunktionierung” both as a key term and in its official approval by the party.