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Recent advances in single particle tracking and supercomputing techniques demonstrate the emergence of normal or anomalous, viscoelastic diffusion in conjunction with non-Gaussian distributions in soft, biological, and active matter systems. We here formulate a stochastic model based on a generalised Langevin equation in which non-Gaussian shapes of the probability density function and normal or anomalous diffusion have a common origin, namely a random parametrisation of the stochastic force. We perform a detailed analysis demonstrating how various types of parameter distributions for the memory kernel result in exponential, power law, or power-log law tails of the memory functions. The studied system is also shown to exhibit a further unusual property: the velocity has a Gaussian one point probability density but non-Gaussian joint distributions. This behaviour is reflected in the relaxation from a Gaussian to a non-Gaussian distribution observed for the position variable. We show that our theoretical results are in excellent agreement with stochastic simulations.
Quantitative estimates of sea-level rise in the Mediterranean Basin become increasingly accurate thanks to detailed satellite monitoring. However, such measuring campaigns cover several years to decades, while longer-term sea-level records are rare for the Mediterranean. We used a data archeological approach to reanalyze monthly mean sea-level data of the Antalya-I (1935–1977) tide gauge to fill this gap. We checked the accuracy and reliability of these data before merging them with the more recent records of the Antalya-II (1985–2009) tide gauge, accounting for an eight-year hiatus. We obtain a composite time series of monthly and annual mean sea levels spanning some 75 years, providing the longest record for the eastern Mediterranean Basin, and thus an essential tool for studying the region's recent sea-level trends. We estimate a relative mean sea-level rise of 2.2 ± 0.5 mm/year between 1935 and 2008, with an annual variability (expressed here as the standard deviation of the residuals, σresiduals = 41.4 mm) above that at the closest tide gauges (e.g., Thessaloniki, Greece, σresiduals = 29.0 mm). Relative sea-level rise accelerated to 6.0 ± 1.5 mm/year at Antalya-II; we attribute roughly half of this rate (~3.6 mm/year) to tectonic crustal motion and anthropogenic land subsidence. Our study highlights the value of data archeology for recovering and integrating historic tide gauge data for long-term sea-level and climate studies.
Because of political conflicts and climate change, migration will be increased worldwide and integration in host societies is a challenge also for migrants. We hypothesize that migrants, who take up the challenge in a new social environment are taller than migrants who do not pose this challenge. We analyze by a questionnaire possible social, nutritional and ethnic influencing factors to body height (BH) of adult offspring of Turkish migrants (n = 82, 39 males) aged from 18 to 34 years (mean age 24.6 years). The results of multiple regression (downward selection) show that the more a male adult offspring of Turkish migrants feels like belonging to the Turkish culture, the smaller he is (95% CI, -3.79, -0.323). Further, the more a male adult offspring of Turkish migrants feels like belonging to the German culture, the taller he is (95% CI, -0.152, 1.738). We discussed it comparable to primates taking up their challenge in dominance, where as a result their body size increase is associated with higher IGF-1 level. IGF-1 is associated with emotional belonging and has a fundamental role in the regulation of metabolism and growth of the human body. With all pilot characteristics of our study results show that the successful challenge of integration in a new society is strongly associated with the emotional integration and identification in the sense of a personal sense of belonging to society. We discuss taller BH as a signal of social growth adjustment. In this sense, a secular trend of BH adaptation of migrants to hosts is a sign of integration.
In this study, the spatial and temporal impacts of the Ataturk Dam on agro-meteorological aspects of the Southeastern Anatolia region have been investigated. Change detection and environmental impacts due to water-reserve changes in Ataturk Dam Lake have been determined and evaluated using multi-temporal Landsat satellite imageries and meteorological datasets within a period of 1984-2011. These time series have been evaluated for three time periods. Dam construction period constitutes the first part of the study. Land cover/use changes especially on agricultural fields under the Ataturk Dam Lake and its vicinity have been identified between the periods of 1984-1992. The second period comprises the 10-year period after the completion of filling up the reservoir in 1992. At this period, Landsat and meteorological time-series analyses are examined to assess the impact of the Ataturk Dam Lake on selected irrigated agricultural areas. For the last 9-year period from 2002 to 2011, the relationships between seasonal water-reserve changes and irrigated plains under changing climatic factors primarily driving vegetation activity (monthly, seasonal, and annual fluctuations of rainfall rate, air temperature, humidity) on the watershed have been investigated using a 30-year meteorological time series. The results showed that approximately 368 km(2) of agricultural fields have been affected because of inundation due to the Ataturk Dam Lake. However, irrigated agricultural fields have been increased by 56.3% of the total area (1552 of 2756 km(2)) on Harran Plain within the period of 1984-2011.
We present the fabrication of TiO2 nanotube electrodes with high biocompatibility and extraordinary spectroscopic properties. Intense surface-enhanced resonance Raman signals of the heme unit of the redox enzyme Cytochromeb(5) were observed upon covalent immobilization of the protein matrix on the TiO2 surface, revealing overall preserved structural integrity and redox behavior. The enhancement factor could be rationally controlled by varying the electrode annealing temperature, reaching a record maximum value of over 70 at 475 degrees C. For the first time, such high values are reported for non-directly surface-interacting probes, for which the involvement of charge-transfer processes in signal amplification can be excluded. The origin of the surface enhancement is exclusively attributed to enhanced localized electric fields resulting from the specific optical properties of the nanotubular geometry of the electrode.
Paleoearthquakes and historic earthquakes are the most important source of information for the estimation of long-term earthquake recurrence intervals in fault zones, because corresponding sequences cover more than one seismic cycle. However, these events are often rare, dating uncertainties are enormous, and missing or misinterpreted events lead to additional problems. In the present study, I assume that the time to the next major earthquake depends on the rate of small and intermediate events between the large ones in terms of a clock change model. Mathematically, this leads to a Brownian passage time distribution for recurrence intervals. I take advantage of an earlier finding that under certain assumptions the aperiodicity of this distribution can be related to the Gutenberg-Richter b value, which can be estimated easily from instrumental seismicity in the region under consideration. In this way, both parameters of the Brownian passage time distribution can be attributed with accessible seismological quantities. This allows to reduce the uncertainties in the estimation of the mean recurrence interval, especially for short paleoearthquake sequences and high dating errors. Using a Bayesian framework for parameter estimation results in a statistical model for earthquake recurrence intervals that assimilates in a simple way paleoearthquake sequences and instrumental data. I present illustrative case studies from Southern California and compare the method with the commonly used approach of exponentially distributed recurrence times based on a stationary Poisson process.
Sub-seasonal thaw slump mass wasting is not consistently energy limited at the landscape scale
(2018)
Predicting future thaw slump activity requires a sound understanding of the atmospheric drivers and geomorphic controls on mass wasting across a range of timescales. On sub-seasonal timescales, sparse measurements indicate that mass wasting at active slumps is often limited by the energy available for melting ground ice, but other factors such as rainfall or the formation of an insulating veneer may also be relevant. To study the sub-seasonal drivers, we derive topographic changes from single-pass radar interferometric data acquired by the TanDEM-X satellites. The estimated elevation changes at 12m resolution complement the commonly observed planimetric retreat rates by providing information on volume losses. Their high vertical precision (around 30 cm), frequent observations (11 days) and large coverage (5000 km(2)) allow us to track mass wasting as drivers such as the available energy change during the summer of 2015 in two study regions. We find that thaw slumps in the Tuktoyaktuk coastlands, Canada, are not energy limited in June, as they undergo limited mass wasting (height loss of around 0 cm day 1) despite the ample available energy, suggesting the widespread presence of early season insulating snow or debris veneer. Later in summer, height losses generally increase (around 3 cm day 1), but they do so in distinct ways. For many slumps, mass wasting tracks the available energy, a temporal pattern that is also observed at coastal yedoma cliffs on the Bykovsky Peninsula, Russia. However, the other two common temporal trajectories are asynchronous with the available energy, as they track strong precipitation events or show a sudden speed-up in late August respectively. The observed temporal patterns are poorly related to slump characteristics like the headwall height. The contrasting temporal behaviour of nearby thaw slumps highlights the importance of complex local and temporally varying controls on mass wasting.
Necrotrophic as well as saprophytic small-spored Altemaria (A.) species are annually responsible for major losses of agricultural products, such as cereal crops, associated with the contamination of food and feedstuff with potential health-endangering Altemaria toxins. Knowledge of the metabolic capabilities of different species-groups to form mycotoxins is of importance for a reliable risk assessment. 93 Altemaria strains belonging to the four species groups Alternaria tenuissima, A. arborescens, A. altemata, and A. infectoria were isolated from winter wheat kernels harvested from fields in Germany and Russia and incubated under equal conditions. Chemical analysis by means of an HPLC-MS/MS multi-Alternaria-toxin-method showed that 95% of all strains were able to form at least one of the targeted 17 non-host specific Altemaria toxins. Simultaneous production of up to 15 (modified) Altemaria toxins by members of the A. tenuissima, A. arborescens, A. altemata species-groups and up to seven toxins by A. infectoria strains was demonstrated. Overall tenuazonic acid was the most extensively formed mycotoxin followed by alternariol and alternariol mono methylether, whereas altertoxin I was the most frequently detected toxin. Sulfoconjugated modifications of alternariol, alternariol mono methylether, altenuisol and altenuene were frequently determined. Unknown perylene quinone derivatives were additionally detected. Strains of the species-group A. infectoria could be segregated from strains of the other three species-groups due to significantly lower toxin levels and the specific production of infectopyrone. Apart from infectopyrone, alterperylenol was also frequently produced by 95% of the A. infectoria strains. Neither by the concentration nor by the composition of the targeted Altemaria toxins a differentiation between the species-groups A. altemata, A. tenuissima and A. arborescens was possible.
Home range size and resource use of breeding and non-breeding white storks along a land use gradient
(2018)
Biotelemetry is increasingly used to study animal movement at high spatial and temporal resolution and guide conservation and resource management. Yet, limited sample sizes and variation in space and habitat use across regions and life stages may compromise robustness of behavioral analyses and subsequent conservation plans. Here, we assessed variation in (i) home range sizes, (ii) home range selection, and (iii) fine-scale resource selection of white storks across breeding status and regions and test model transferability. Three study areas were chosen within the Central German breeding grounds ranging from agricultural to fluvial and marshland. We monitored GPS-locations of 62 adult white storks equipped with solar-charged GPS/3D-acceleration (ACC) transmitters in 2013-2014. Home range sizes were estimated using minimum convex polygons. Generalized linear mixed models were used to assess home range selection and fine-scale resource selection by relating the home ranges and foraging sites to Corine habitat variables and normalized difference vegetation index in a presence/pseudo-absence design. We found strong variation in home range sizes across breeding stages with significantly larger home ranges in non-breeding compared to breeding white storks, but no variation between regions. Home range selection models had high explanatory power and well predicted overall density of Central German white stork breeding pairs. Also, they showed good transferability across regions and breeding status although variable importance varied considerably. Fine-scale resource selection models showed low explanatory power. Resource preferences differed both across breeding status and across regions, and model transferability was poor. Our results indicate that habitat selection of wild animals may vary considerably within and between populations, and is highly scale dependent. Thereby, home range scale analyses show higher robustness whereas fine-scale resource selection is not easily predictable and not transferable across life stages and regions. Such variation may compromise management decisions when based on data of limited sample size or limited regional coverage. We thus recommend home range scale analyses and sampling designs that cover diverse regional landscapes and ensure robust estimates of habitat suitability to conserve wild animal populations.
Anti-fat bias is widespread and is linked to the internalization of weight bias and psychosocial problems. The purpose of this study was to examine the internalization of weight bias among children across weight categories and to evaluate the psychometric properties of the Weight Bias Internalization Scale for Children (WBIS-C). Data were collected from 1484 primary school children and their parents. WBIS-C demonstrated good internal consistency (alpha = .86) after exclusion of Item 1. The unitary factor structure was supported using exploratory and confirmatory factor analyses (factorial validity). Girls and overweight children reported higher WBIS-C scores in comparison to boys and non-overweight peers (known-groups validity). Convergent validity was shown by significant correlations with psychosocial problems. Internalization of weight bias explained additional variance in different indicators of psychosocial well-being. The results suggest that the WBIS-C is a psychometrically sound and informative tool to assess weight bias internalization among children.
Die Gesundheit unserer Jugend ist seit je ein gesellschaftspolitisches Primat und verdient die grösstmögliche Beachtung. Ein Teilbereich, nämlich Bewegung und Sport, ist in der Schweiz auch aus diesem Grund verfassungsmässig geregelt. Sämtliche Volksschulen müssen bis ins neunte Schuljahr pro Woche drei Lektionen Bewegung und Sport anbieten.. Als einziges Schulfach geniesst Bewegung und Sport diesen bundesgesetzlichen Support im sonst streng föderalistisch organisierten Bildungssystem der Schweiz. Trotz diesen drei verordneten Sportlektionen ist die physische Leistungsfähigkeit unserer Jugend einhergehend mit gesundheitlichen Parametern seit 1985 rückläufig und seit ein paar Jahren auf tiefem Niveau stagnierend. Zudem berichten Lehrpersonen über sinkende Konzentrationsfähigkeit in den letzten Jahren. Um eine flächendeckende Verbesserung der Situation zu bewirken, bietet sich die Schule als zentraler Ort der Einflussnahme an. Dies gilt im Besonderen für den Bereich Bewegung und Sport. Im Jahr 2005 wurde das Programm einer täglichen Bewegungs- und Sportstunde an der Primarschule in Luzern/Schweiz gestartet. Nach einem kontinuierlichen Ausbau kamen ab 2011 etwas über 1300 Kinder von der ersten bis zur sechsten Klasse in den Genuss dieser täglichen Bewegungslektion. Die wissenschaftlichen Untersuchungen in den drei gesellschaftlich hoch relevanten Bereichen der Konzentrationsfähigkeit, des Übergewichts und der Gleichgewichtsfähigkeit ergaben positive Resultate. So konnte die Konzentrationsfähigkeit – die Basis für erfolgreiches Lernen – signifikant gesteigert werden und teilweise signifikant war die Verbesserung des statischen Gleichgewichts. Ein positiver Trend zeigte sich auch bei der Senkung des Body-Mass-Indexes bei Knaben. Dies konnte bei den Mädchen nicht nachgewiesen werden. Auch wenn nicht alle Hypothesen vollumfänglich bestätigt werden konnten, gilt es festzuhalten, dass das Projekt der täglichen Sport- und Bewegungsstunde die Erwartungen in allen drei Messbereichen erfüllt hat und die Verbesserungen hinsichtlich der Konzentrationsfähigkeit, des Übergewichts und der Gleichgewichtsfähigkeit mehrheitlich ausgewiesen werden können. Es lohnt sich also, die tägliche Sport- und Bewegungsstunde an der Primarschule einzuführen und den Präventionsgedanken auch Taten folgen zu lassen.
The combination of gold nanoparticles with liposomes is important for nano- and biotechnology. Here, we present direct, label-free characterization of liposome structure and composition at the site of its interaction with citrate-stabilized gold nanoparticles by surface-enhanced Raman scattering (SERS) and cryogenic electron microscopy (cryo-EM). Evidenced by the vibrational spectra and cryo-EM, the gold nanoparticles destroy the bilayer structure of interacting liposomes in the presence of a high amount of citrate, while at lower citrate concentration the nanoparticles interact with the surface of the intact liposomes. The spectra of phosphatidylcholine and phosphatidylcholine/sphingomyelin liposomes show that at the site of interaction the lipid chains are in the gel phase. The SERS spectra indicate that cholesterol has strong effects on the contacts of the vesicles with the nanoparticles. By combining cryo-EM and SERS, the structure and properties of lipid nanoparticle composites could be tailored for the development of drug delivery systems.
A straightforward approach for the precise multifunctional surface modification of particles with three-dimensional patches using microcontact printing is presented. By comparison to previous works it was possible to not only control the diameter, but also to finely tune the thickness of the deposited layer, opening up the way for three-dimensional structures and orthogonal multifunctionality. The use of PEI as polymeric ink, PDMS stamps for microcontact printing on silica particles and the influence of different solvents during particle release on the creation of functional particles with three-dimensional patches are described. Finally, by introducing fluorescent properties by incorporation of quantum dots into patches and by particle self-assembly via avidin-biotin coupling, the versatility of this novel modification method is demonstrated.
This publication demonstrates the abilities of a precise and straightforward microcontact printing approach for the preparation of patchy silica particles. In a broad particle size range, it is possible to finely tune the number and parameters of three-dimensional patches like diameter and thickness using only polyethyleneimine ink, poly(dimethoxysilane) as stamp material and a suitable release solvent.
Wird Schon Stimmen!
(2018)
The article puts forward a novel analysis of the German modal particle schon as a modal degree operator over propositional content. The proposed analysis offers a uniform perspective on the semantics of modal schon and its aspectual counterpart meaning ‘already’: Both particles are analyzed as denoting a degree operator, expressing a scale-based comparison over relevant alternatives. The alternatives are determined by focus in the case of aspectual schon (Krifka 2000), but are restricted to the polar alternatives p and ¬p in the case of modal schon. Semantically, modal schon introduces a presupposition to the effect that the circumstantial conversational background contains more factual evidence in favor of p than in favor of ¬p, thereby making modal schon the not at-issue counterpart of the overt comparative form eher ‘rather’ (Herburger & Rubinstein 2014). The analysis incorporates basic insights from earlier analyses of modal schon in a novel way, and it also offers new insights as to the underlying workings of modality in natural language as involving propositions rather than possible worlds (Kratzer 1977, 2012).
Direkte Arylierung
(2018)
Draft Article 15 of the International Law Commission’s project on crimes against humanity — dealing with the settlement of disputes arising from a proposed convention — attempts to strike a balance between state autonomy and robust judicial supervision. It largely follows Article 22 of the Convention on the Elimination of All Forms of Racial Discrimination, which renders the jurisdiction of the International Court of Justice (ICJ) conditional upon prior negotiations. Hence, the substance of the clause can be interpreted in light of the recent case law of the ICJ, especially in the case Georgia v. Russia. In addition, this contribution discusses several issues regarding the scope ratione temporis of the compromissory clause. It advances several proposals to improve the current draft, addressing its relationship with state responsibility — an explicit reference to which is currently missing — as well as the relationship between the ICJ and a possible treaty body. It also proposes to recalibrate the interplay of the requirement of prior negotiations with, respectively, the possibility of seizing a future treaty body and the indication of provisional measures by the ICJ.
On 14 December 2017, the Assembly of States Parties of the Rome Statute decided to activate the International Criminal Court’s jurisdiction over the crime of aggression. In doing so, it however seems to have rescinded the Kampala amendment adopted in 2010, and in particular, the need for State Parties to eventually opt out from the Court’s aggression-related jurisdiction. This reversal, while being more in line with the Rome Statute than the Kampala amendment itself, raises new (and old) and challenging legal questions which are highlighted in this article.
Understanding the geologic evolution of Northern Tibetan Plateau with multiple thermochronometers
(2018)
The early onset of deformation following the India-Asia collision, Neogene expanse of uplift, and complex systems that comprise strike-slip faults, thrust faults, and intermontane basins characterize the Cenozoic tectonism of Northern Tibetan Plateau and raise two prominent questions in orogenic geodynamics: 1) What mechanism(s) control(s) the transfer of stress related to the India-Asia collision across the distance of >2000 km; and 2) Why the development of high topography was delayed in the Northern Tibetan Plateau and what does it reveal about how the internal forces and external boundary conditions evolved. To address these two questions, we reconstruct a holistic spatial-temporal deformation history of the Northern Tibetan Plateau by using a range of thermochronometers, with closure temperature spanning from 350 degrees C to-60-70 degrees C. This multi-thermochronometer study reveals three stages of faulting related cooling, in the early Cretaceous, in Paleocene-Eocene and in middle-late Miocene. We observe that Paleocene-Eocene deformation was spatially restricted and mostly occurred on reactivated Cretaceous structures, indicating a control of pre-existing weakness on early Cenozoic deformation. Extensive Neogene deformation contrasts with restricted Paleocene-Eocene deformation and relatively quiescent shortening during the Oligocene-early Miocene, which implies a change in the regional tectonics regime. Global plate reconstructions show that this tectonic reorganization is coeval with an increase in Pacific-Asia plate convergence rates. We argue that this change in regional tectonics is a result of increasing constrictive environment of the eastern plate boundary, which changed the behavior of the Altyn Tagh fault the boundary fault of Northern Tibetan Plateau, causing it to change from feeding slip into structures out of the plateau to feeding slip into structures at plateau margins.
Whistler mode exohiss are the structureless hiss waves observed outside the plasma pause with featured equatorward Poynting flux. An event of the amplification of exohiss as well as chorus waves was recorded by Van Allen Probes during the recovery phase of a weak geomagnetic storm. Amplitudes of both types of the waves showed a significant increase at the regions of electron density enhancements. It is found that the electrons resonant with exohiss and chorus showed moderate pitch angle anisotropies. The ratio of the number of electrons resonating with exohiss to total electron number presented in-phase correlation with density variations, which suggests that exohiss can be amplified due to electron density enhancement in terms of cyclotron instability. The calculation of linear growth rates further supports above conclusion. We suggest that exohiss waves have potential to become more significant due to the background plasma fluctuation.
Mimicking non-verbal emotional expressions and empathy development in simulated consultations
(2018)
Objective: To explore the feasibility of applying an experimental design to study the relationship between non-verbal emotions and empathy development in simulated consultations.
Method: In video-recorded simulated consultations, twenty clinicians were randomly allocated to either an experimental group (instructed to mimic non-verbal emotions of a simulated patient, SP) or a control group (no such instruction). Baseline empathy scores were obtained before consultation, relational empathy was rated by SP after consultation. Multilevel logistic regression modelled the probability of mimicry occurrence, controlling for baseline empathy and clinical experience. ANCOVA compared group differences on relational empathy and consultation smoothness.
Results: Instructed mimicry lasted longer than spontaneous mimicry. Mimicry was marginally related to improved relational empathy. SP felt being treated more like a whole person during consultations with spontaneous mimicry. Clinicians who displayed spontaneous mimicry felt consultations went more smoothly.
Conclusion: The experimental approach improved our understanding of how non-verbal emotional mimicry contributed to relational empathy development during consultations. Further work should ascertain the potential of instructed mimicry to enhance empathy development.
Practice implications: Understanding how non-verbal emotional mimicry impacts on patients’ perceived clinician empathy during consultations may inform training and intervention programme development.
During sentence reading, low spatial frequency information afforded by spaces between words is the primary factor for eye guidance in spaced writing systems, whereas saccade generation for unspaced writing systems is less clear and under debate. In the present study, we investigated whether word-boundary information, provided by alternating colors (consistent or inconsistent with word-boundary information) influences saccade-target selection in Chinese. In Experiment 1, as compared to a baseline (i.e., uniform color) condition, word segmentation with alternating color shifted fixation location towards the center of words. In contrast, incorrect word segmentation shifted fixation location towards the beginning of words. In Experiment 2, we used a gaze-contingent paradigm to restrict the color manipulation only to the upcoming parafoveal words and replicated the results, including fixation location effects, as observed in Experiment 1. These results indicate that Chinese readers are capable of making use of parafoveal word-boundary knowledge for saccade generation, even if such information is unfamiliar to them. The present study provides novel support for the hypothesis that word segmentation is involved in the decision about where to fixate next during Chinese reading.
The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)(3)) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)(3) films show a transition temperature (TT) at 33 degrees C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)(3) films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)(3). However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)(3) films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)(3) films depends on the final temperature. It decreases from (9.7 +/- 0.3)% to (7.0 +/- 0.3)% or (6.0 +/- 0.3)% when the final temperatures are set to 35 degrees C, 45 degrees C and 50 degrees C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.
Melanoma represents a prime example demonstrating the success of targeted therapy in cancer. Nevertheless, it remained a deadly disease until now, and the identification of new, independent strategies as well as the understanding of their molecular mechanisms may help to finally overcome the high mortality. Both indirubins and TNF-related apoptosis-inducing ligand (TRAIL) represent promising candidates. Here, the indirubin derivative DKP-073 is shown to trigger apoptosis in melanoma cells, which is enhanced by the combination with TRAIL and is accompanied by complete loss of cell viability. Addressing the signaling cascade, characteristic molecular steps were identified as caspase-3 activation, downregulation of XIAP, upregulation of p53 and TRAIL receptor 2, loss of mitochondrial membrane potential, and STAT-3 dephosphorylation. The decisive step, however, turned out to be the early production of ROS already at 1 h. This was proven by antioxidant pretreatment, which completely abolished apoptosis induction and loss of cell viability as well as abrogated all signaling effects listed above. Thus, ROS appeared as upstream of all proapoptotic signaling. The data indicate a dominant role of ROS in apoptosis regulation, and the new pathway may expose a possible Achilles heel of melanoma.
We show that a combined action of noise and delayed feedback on an excitable theta-neuron leads to rather coherent stochastic bursting. An idealized point process, valid if the characteristic timescales in the problem are well separated, is used to describe statistical properties such as the power spectral density and the interspike interval distribution. We show how the main parameters of the point process, the spontaneous excitation rate, and the probability to induce a spike during the delay action can be calculated from the solutions of a stationary and a forced Fokker-Planck equation.
Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization. Herein, we discover that during polymerization hydrogen sulfide evolves from the hydrolysis of carbonyl sulfide, which is the byproduct of ring-opening reaction, and reacts with NNTA to produce cyclic oligopeptoids. The capture of N-ethylethanethioic acid as an intermediate product confirms the reaction mechanism together with density functional theory quantum computational results. By bubbling the polymerization solution with argon, the side reaction can be suppressed to allow the synthesis of polysarcosine with high molar mass (M-n = 11,200 g/mol, D = 1.25) even in the presence of similar to 10,000 ppm of water.
The process of leaf senescence consists of the final stage of leaf development. It has evolved as a mechanism to degrade macromolecules and micronutrients and remobilize them to other developing parts of the plant; hence it plays a central role for the survival of plants and crop production. During senescence, a range of physiological, morphological, cellular, and molecular events occur, which are generally referred to as the senescence syndrome that includes several hallmarks such as visible yellowing, loss of chlorophyll and water content, increase of ion leakage and cell death, deformation of chloroplast and cell structure, as well as the upregulation of thousands of so-called senescence-associated genes (SAGs) and downregulation of photosynthesis-associated genes (PAGs). This chapter is devoted to methods characterizing the onset and progression of leaf senescence at the morphological, physiological, cellular, and molecular levels. Leaf senescence normally progresses in an age-dependent manner but is also induced prematurely by a variety of environmental stresses in plants. Focused on the hallmarks of the senescence syndrome, a series of protocols is described to asses quantitatively the senescence process caused by developmental cues or environmental perturbations. We first briefly describe the senescence process, the events associated with the senescence syndrome, and the theories and methods to phenotype senescence. Detailed protocols for monitoring senescence in planta and in vitro, using the whole plant and the detached leaf, respectively, are presented. For convenience, most of the protocols use the model plant species Arabidopsis and rice, but they can be easily extended to other plants.
The Gongjue basin from the eastern Qiangtang terrane is located in the transition region where the regional structural lineation curves from east-west-oriented in Tibet to north-south-oriented in Yunnan. In this study, we sampled the red beds in the basin from the lower Gongjue to upper Ranmugou formations for the first time covering the entire stratigraphic profile. The stratigraphic ages are bracketed within 53-43Ma by new detrital zircon U-Pb ages constraining the maximum deposition age to 52.51.5Ma. Rock magnetic and petrographic studies indicate that detrital magnetite and hematite are the magnetic carriers. Positive reversals and fold tests demonstrate that the characteristic remanent magnetization has a primary origin. The Gongjue and Ranmugou formations yield mean characteristic remanent magnetization directions of D-s/I-s=31.0 degrees/21.3 degrees and D-s/I-s=15.9 degrees/22.0 degrees, respectively. The magnetic inclination of these characteristic remanent magnetizations is significantly shallowed compared to the expected inclination for the locality. However, the elongation/inclination correction method does not provide a meaningful correction, likely because of syn-depositional rotation. Rotations relative to the Eurasian apparent polar wander path occurred in three stages: Stage I, 33.33.4 degrees clockwise rotation during the deposition of the Gongjue and lower Ranmugou formations; Stage II, 26.93.7 degrees counterclockwise rotation during deposition of the lower and middle Ranmugou formation; and Stage III, 17.73.3 degrees clockwise rotation after 43Ma. The complex rotation history recorded in the basin is possibly linked to sinistral shear along the Qiangtang block during India indentation into Asia and the early stage of the extrusion of the northwestern Indochina blocks away from eastern Tibet.
Molecularly imprinted polymer (MP) nanofilrns for transferrin (Trf) have been synthesized on gold surfaces by electro-polymerizing the functional monomer scopoletin in the presence of the protein target or around pre-adsorbed Trf. As determined by atomic force microscopy (AFM) the film thickness was comparable with the molecular dimension of the target. The target (re)binding properties of the electro-synthesized MIP films was evaluated by cyclic voltammetry (CV) and square wave voltammetry (SWV) through the target-binding induced permeability changes of the MIP nanofilms to the ferricyanide redox marker, as well as by surface plasmon resonance (SPR) and surface enhanced infrared absorption spectroscopy (SEIRAS) of the immobilized protein molecules. For Trf a linear concentration dependence in the lower micromolar range and an imprinting factor of similar to 5 was obtained by SWV and SPR. Furthermore, non-target proteins including the iron-free apo-Trf were discriminated by pronounced size and shape specificity. Whilst it is generally assumed that the rebinding of the target or of cross-reacting proteins exclusively takes place at the polymer here we considered also the interaction of the protein molecules with the underlying gold transducers. We demonstrate by SWV that adsorption of proteins suppresses the signal of the redox marker even at the bare gold surface and by SEIRAS that the treatment of the MIP with proteinase K or NaOH only partially removes the target protein. Therefore, we conclude that when interpreting binding of proteins to directly MIP-covered gold electrodes the interactions between the protein and the gold surface should also be considered.
Engineering the interface between the perovskite absorber and the charge-transporting layers has become an important method for improving the charge extraction and open-circuit voltage (V-OC) of hybrid perovskite solar cells. Conjugated polymers are particularly suited to form the hole-transporting layer, but their hydrophobicity renders it difficult to solution-process the perovskite absorber on top. Herein, oxygen plasma treatment is introduced as a simple means to change the surface energy and work function of hydrophobic polymer interlayers for use as p-contacts in perovskite solar cells. We find that upon oxygen plasma treatment, the hydrophobic surfaces of different prototypical p-type polymers became sufficiently hydrophilic to enable subsequent perovskite junction processing. In addition, the oxygen plasma treatment also increased the ionization potential of the polymer such that it became closer to the valance band energy of the perovskite. It was also found that the oxygen plasma treatment could increase the electrical conductivity of the p-type polymers, facilitating more efficient charge extraction. On the basis of this concept, inverted MAPbI(3) perovskite devices with different oxygen plasma-treated polymers such as P3HT, P3OT, polyTPD, or PTAA were fabricated with power conversion efficiencies of up to 19%.
The ongoing trend of miniaturizing multifunctional devices, especially for minimally-invasive medical or sensor applications demands new strategies for designing the required functional polymeric micro-components or micro-devices. Here, polymers, which are capable of active movement, when an external stimulus is applied (e.g. shape-memory polymers), are intensively discussed as promising material candidates for realization of multifunctional micro-components. In this context further research activities are needed to gain a better knowledge about the underlying working principles for functionalization of polymeric micro-scale objects with a shape-memory effect. First reports about electrospun solid microfiber scaffolds, demonstrated a much more pronounced shape-memory effect than their bulk counterparts, indicating the high potential of electrospun micro-objects.
Based on these initial findings this thesis was aimed at exploring whether the alteration of the geometry of micro-scale electrospun polymeric objects can serve as suitable parameter to tailor their shape-memory properties. The central hypothesis was that different geometries should result in different degrees of macromolecular chain orientation in the polymeric micro-scale objects, which will influence their mechanical properties as well as thermally-induced shape-memory function. As electrospun micro-scale objects, microfiber scaffolds composed of hollow microfibers with different wall thickness and electrosprayed microparticles as well as their magneto-sensitive nanocomposites all prepared from the same polymer exhibiting pronounced bulk shape-memory properties were investigated. For this work a thermoplastic multiblock copolymer, named PDC, with excellent bulk shape-memory properties, associated with crystallizable oligo(ε-caprolactone) (OCL) switching domains, was chosen for the preparation of electrospun micro-scale objects, while crystallizable oligo(p-dioxanone) (OPDO) segments serve as hard domains in PDC.
In the first part of the thesis microfiber scaffolds with different microfiber geometries (solid or hollow with different wall thickness) were discussed. Hollow microfiber based PDC scaffolds were prepared by coaxial electrospinning from a 1, 1, 1, 3, 3, 3 hexafluoro-2-propanol (HFP) solution with a polymer concentration of 13% w·v-1. Here as a first step core-shell fiber scaffolds consisting of microfibers with a PDC shell and sacrificial poly(ethylene glycol) (PEG) core are generated. The hollow PDC microfibers were achieved after dissolving the PEG core with water. The utilization of a fixed electrospinning setup and the same polymer concentration of the PDC spinning solution could ensure the fabrication of microfibers with almost identical outer diameters of 1.4 ± 0.3 µm as determined by scanning electron microscopy (SEM). Different hollow microfiber wall thicknesses of 0.5 ± 0.2 and 0.3 ± 0.2 µm (analyzed by SEM) have been realized by variation of the mass flow rate, while solid microfibers were obtained by coaxial electrospinning without supplying any core solution. Differential scanning calorimetry experiments and tensile tests at ambient temperature revealed an increase in degree of OCL crystallinity form χc,OCL = 34 ± 1% to 43 ± 1% and a decrease in elongation of break from 800 ± 40% to 200 ± 50% associated with an increase in Young´s modulus and failture stress for PDC hollow microfiber scaffolds when compared with soild fibers. The observed effects were enhanced with decreasing wall thickness of the single hollow fibers. The shape-memory properties of the electrospun PDC scaffolds were quantified by cyclic, thermomechanical tensile tests. Here, scaffolds comprising hollow microfibers exhibited lower shape fixity ratios around Rf = 82 ± 1% and higher shape recovery ratios of Rr = 67 ± 1% associated to more pronounced relaxation at constant strain during the first test cycle and a lower switching temperature of Tsw = 33 ± 1 °C than the fibrous meshes consisting of solid microfibers. These findings strongly support the central hypothesis that different fiber geometries (solid or hollow with different wall thickness) in electrospun scaffolds result in different degrees of macromolecular chain orientation in the polymeric micro-scale objects, which can be applied as design parameter for tailoring their mechanical and shape-memory properties.
The second part of the thesis deals with electrosprayed particulate PDC micro-scale objects. Almost spherical PDC microparticles with diameters of 3.9 ± 0.9 μm (as determined by SEM) were achieved by electrospraying of HFP solution with a polymer concentration of 2% w·v-1. In contrast, smaller particles with sizes of 400 ± 100 nm or 1.2 ± 0.3 μm were obtained for the magneto-sensitive composite PDC microparticles containing 23 ± 0.5 wt% superparamagnetic magnetite nanoparticles (mNPs). All prepared PDC microparticles exhibited a similar overall crystallinity like the PDC bulk material as analyzed by DSC. AFM nanoindentation results revealed no influence of the nanofiller incorporation on the local mechanical properties represented by the reduced modulus determined for pure PDC microparticles and magneto-sensitive composite PDC microparticles with similar diameters around 1.3 µm. It was found that the reduced modulus of the nanocomposite microparticles increased substantially with decreasing particles size from 2.4 ± 0.9 GPa (1.2 µm) to 11.9 ± 3.1 GPa (0.4 µm), which can be related to a higher orientation of the macromolecules at the surface of smaller sized microparticles. The magneto-sensitivity of such nanocomposite microparticles could be demonstrated in two aspects. One was by attracting/collecting the composite micro-objects with an external permanent magnet. The other one was by a inductive heating to 44 ± 1 °C, which is well above the melting transition of the OCL switching domains, when compacted to a 10 x 10 mm2 film with a thickness of 10 µm and exposed to an alternating magnet field with an magnetic field strength of 30 kA·m-1. Both functions are of great relevance for designing next generation drug delivery systems combining targeting and on demand release.
By a compression approach shape-memory functionalization of individual microparticles could be realized. Here different programming pressures and compression temperatures were applied. The shape-recovery capability of the programmed PDC microparticles was quantified by online and off-line heating experiments analyzed via microscopy measurement. The obtained shape-memory properties were found to be strongly depending on the applied programming pressure and temperature. The best shape-memory performance with a high shape recovery rate of about Rr = 80±1% was obtained when a low pressure of 0.2 MPa was applied at 55 °C. Finally, it was demonstrated that PDC microparticles can be utilized as micro building parts for preparation of a macroscopic film with temporary stability by compression of a densely packed array of PDC microparticles at 60 °C followed by subsequent cooling to ambient temperature. This film disintegrates into individual microparticles upon heating to 60 °C. Based on this technology the design of stable macroscopic release systems can be envisioned, which can be easily fixed at the site of treatment (i.e. by suturing) and disintegrate on demand to microparticles facilitating the drug release.
In summary, the results of this thesis could confirm the central hypothesis that the variation of the geometry of polymeric micro-objects is a suitable parameter to adjust their shape-memory performance by changing the degree of macromolecular chain orientation in the specimens or by enabling new functions like on demand disintegration. These fundamental findings might be relevant for designing novel miniaturized multifunctional polymer-based devices.
Spectroscopic observations play essential roles in astrophysics. They are crucial for determining physical parameters in our Universe, providing information about the chemistry of various astronomical environments. The proper execution of the spectroscopic analysis requires accounting for all the physical effects that are compatible to the signal-to-noise ratio. We find in this paper the influence on spectroscopy from the atomic/ground state alignment owing to anisotropic radiation and modulated by interstellar magnetic field, has significant impact on the study of interstellar gas. In different observational scenarios, we comprehensively demonstrate how atomic alignment influences the spectral analysis and provide the expressions for correcting the effect. The variations are even more pronounced for multiplets and line ratios. We show the variation of the deduced physical parameters caused by the atomic alignment effect, including alpha-to-iron ratio ([X/Fe]) and ionization fraction. Synthetic observations are performed to illustrate the visibility of such effect with current facilities. A study of Photodissociation regions in rho Ophiuchi cloud is presented to demonstrate how to account for atomic alignment in practice. Our work has shown that due to its potential impact, atomic alignment has to be included in an accurate spectroscopic analysis of the interstellar gas with current observational capability.
Magnetic fields play important roles in many astrophysical processes. However, there is no universal diagnostic for the magnetic fields in the interstellar medium (ISM) and each magnetic tracer has its limitation. Any new detection method is thus valuable. Theoretical studies have shown that submillimetre fine-structure lines are polarized due to atomic alignment by ultraviolet photon-excitation, which opens up a new avenue to probe interstellar magnetic fields. We will, for the first time, perform synthetic observations on the simulated three-dimensional ISM to demonstrate the measurability of the polarization of submillimetre atomic lines. The maximum polarization for different absorption and emission lines expected from various sources, including star-forming regions are provided. Our results demonstrate that the polarization of submillimetre atomic lines is a powerful magnetic tracer and add great value to the observational studies of the submilimetre astronomy.
Cell-free protein synthesis as a novel tool for directed glycoengineering of active erythropoietin
(2018)
As one of the most complex post-translational modification, glycosylation is widely involved in cell adhesion, cell proliferation and immune response. Nevertheless glycoproteins with an identical polypeptide backbone mostly differ in their glycosylation patterns. Due to this heterogeneity, the mapping of different glycosylation patterns to their associated function is nearly impossible. In the last years, glycoengineering tools including cell line engineering, chemoenzymatic remodeling and site-specific glycosylation have attracted increasing interest. The therapeutic hormone erythropoietin (EPO) has been investigated in particular by various groups to establish a production process resulting in a defined glycosylation pattern. However commercially available recombinant human EPO shows batch-to-batch variations in its glycoforms. Therefore we present an alternative method for the synthesis of active glycosylated EPO with an engineered O-glycosylation site by combining eukaryotic cell-free protein synthesis and site-directed incorporation of non-canonical amino acids with subsequent chemoselective modifications.
We investigated the influence of the emitter (amorphous-Si, a-Si, or polythiophene derivatives: poly(3-hexylthiophene), P3HT, and poly(3-[3,6-dioxaheptyl]-thiophene), P3DOT) and the interface passivation (intrinsic a-Si or SiOX and methyl groups or SiOX) on the c-Si based 1 × 1 cm2 planar hybrid heterojunction solar cell parameters. We observed higher short circuit currents for the P3HT or P3DOT/c-Si solar cells than those obtained for a-Si/c-Si devices, independent of the interface passivation. The obtained VOC of 659 mV for the P3DOT/SiOX/c-Si heterojunction solar cell with hydrophilic 3,6-dioxaheptyl side chains is among the highest reported for c-Si/polythiophene devices. The maximum power conversion efficiency, PCE, was 11% for the P3DOT/SiOX/c-Si heterojunction solar cell. Additionally, our wafer lifetime measurements reveal a field effect passivation in the wafer induced by the polythiophenes when deposited on c-Si.
The Cretaceous units exposed in the northwestern segment of the Colombian Andes preserve the record of extensional and compressional tectonics prior to the collision with Caribbean oceanic terranes. We integrated field, stratigraphic, sedimentary provenance, whole rock geochemistry, Nd isotopes and U-Pb zircon data to understand the Cretaceous tectonostratigraphic and magmatic record of the Colombian Andes. The results suggest that several sedimentary successions including the Abejorral Fm. were deposited on top of the continental basement in an Early Cretaceous backarc basin (150-100 Ma). Between 120 and 100 Ma, the appearance of basaltic and andesitic magmatism (similar to 115-100 Ma), basin deepening, and seafloor spreading were the result of advanced stages of backarc extension. A change to compressional tectonics took place during the Late Cretaceous (100-80 Ma). During this compressional phase, the extended blocks were reincorporated into the margin, closing the former Early Cretaceous backarc basin. Subsequently, a Late Cretaceous volcanic arc was built on the continental margin: as a result, the volcanic rocks of the Quebradagrande Complex were unconformably deposited on top of the faulted and folded rocks of the Abejorral Fm. Between the Late Cretaceous and the Paleocene (80-60 Ma), an arc-continent collision between the Caribbean oceanic plateau and the South-American continental margin deformed the rocks of the Quebradagrande Complex and shut-down the active volcanic arc. Our results suggest an Early Cretaceous extensional event followed by compressional tectonics prior to the collision with the Caribbean oceanic plateau. (C) 2019 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.
Recent treatment protocols have been successful in improving working memory (WM) in individuals with aphasia. However, the evidence to date is small and the extent to which improvements in trained tasks of WM transfer to untrained memory tasks, spoken sentence comprehension, and functional communication is yet poorly understood. To address these issues, we conducted a multiple baseline study with three German-speaking individuals with chronic post stroke aphasia. Participants practised two computerised WM tasks (n-back with pictures and aback with spoken words) four times a week for a month, targeting two WM processes: updating WM representations and resolving interference. All participants showed improvement on at least one measure of spoken sentence comprehension and everyday memory activities. Two of them showed improvement also on measures of WM and functional communication. Our results suggest that WM can be improved through computerised training in chronic aphasia and this can transfer to spoken sentence comprehension and functional communication in some individuals.
Due to the low cutaneous bioavailability of tacrolimus (TAC), penetration enhancers are used to improve its penetration into the skin. However, poor loading capacity, non-biodegradability, toxicity, and in some cases inefficient skin penetration are challenging issues that hamper their applications for the dermal TAC delivery. Here we present poly(lactide-co-glycerol) (PLG) as a water soluble, biodegradable, and biocompatible TAC-carrier with high loading capacity (14.5% w/w for TAC) and high drug delivery efficiencies into the skin. PLG was synthesized by cationic ring-opening copolymerization of a mixture of glycidol and lactide and showed 35 nm and 300 nm average sizes in aqueous solutions before and after loading of TAC, respectively. Delivery experiments on human skin, quantified by fluorescence microscopy and LC-MS/MS, showed a high ability for PLG to deposit Nile red and TAC into the stratum corneum and viable epidermis of skin in comparison with Protopic (R) (0.03% w/w, TAC ointment). The cutaneous distribution profile of delivered TAC proved that 80%, 16%, and 4% of the cutaneous drug level was deposited in the stratum corneum, viable epidermis, and upper dermis, respectively. TAC delivered by PLG was able to efficiently decrease the IL-2 and TSLP expressions in human skin models. Taking advantage of the excellent physicochemical and biological properties of PLG, it can be used for efficient dermal TAC delivery and potential treatment of inflammatory skin diseases.
Ubiquitous business processes are the new generation of processes that pervade the physical space and interact with their environments using a minimum of human involvement. Although they are now widely deployed in the industry, their deployment is still ad hoc . They are implemented after an arbitrary modeling phase or no modeling phase at all. The absence of a solid modeling phase backing up the implementation generates many loopholes that are stressed in the literature. Here, we tackle the issue of modeling ubiquitous business processes. We propose patterns to represent the recent ubiquitous computing features. These patterns are the outcome of an analysis we conducted in the field of human-computer interaction to examine how the features are actually deployed. The patterns' understandability, ease-of-use, usefulness, and completeness are examined via a user experiment. The results indicate that these four indexes are on the positive track. Hence, the patterns may be the backbone of ubiquitous business process modeling in industrial applications.
X-ray free-electron lasers (XFELs) and table-top sources of x-rays based upon high harmonic generation (HHG) have revolutionized the field of ultrafast x-ray atomic and molecular physics, largely due to an explosive growth in capabilities in the past decade. XFELs now provide unprecedented intensity (10(20) W cm(-2)) of x-rays at wavelengths down to similar to 1 Angstrom, and HHG provides unprecedented time resolution (similar to 50 attoseconds) and a correspondingly large coherent bandwidth at longer wavelengths. For context, timescales can be referenced to the Bohr orbital period in hydrogen atom of 150 attoseconds and the hydrogen-molecule vibrational period of 8 femtoseconds; wavelength scales can be referenced to the chemically significant carbon K-edge at a photon energy of similar to 280 eV (44 Angstroms) and the bond length in methane of similar to 1 Angstrom. With these modern x-ray sources one now has the ability to focus on individual atoms, even when embedded in a complex molecule, and view electronic and nuclear motion on their intrinsic scales (attoseconds and Angstroms). These sources have enabled coherent diffractive imaging, where one can image non-crystalline objects in three dimensions on ultrafast timescales, potentially with atomic resolution. The unprecedented intensity available with XFELs has opened new fields of multiphoton and nonlinear x-ray physics where behavior of matter under extreme conditions can be explored. The unprecedented time resolution and pulse synchronization provided by HHG sources has kindled fundamental investigations of time delays in photoionization, charge migration in molecules, and dynamics near conical intersections that are foundational to AMO physics and chemistry. This roadmap coincides with the year when three new XFEL facilities, operating at Angstrom wavelengths, opened for users (European XFEL, Swiss-FEL and PAL-FEL in Korea) almost doubling the present worldwide number of XFELs, and documents the remarkable progress in HHG capabilities since its discovery roughly 30 years ago, showcasing experiments in AMO physics and other applications. Here we capture the perspectives of 17 leading groups and organize the contributions into four categories: ultrafast molecular dynamics, multidimensional x-ray spectroscopies; high-intensity x-ray phenomena; attosecond x-ray science.
The Gezi uprising can be considered a crucial turning in Turkish politics. As a response to countrywide democratic protests, the Justice and Development Party (AKP) government revived the security state, escalated authoritarian tendencies, and started to organize a nationalist, Islamist, and conservative backlash. This essay argues that the Gezi Park protests revealed both the fragility of the AKP's hegemony and the limits of the dominant political group habitus, which were promoted by the party to consolidate political polarization in favor of the party's hegemony. Moreover, it is argued that the Gezi uprising transformed the culture of political protests in the country and paved the way for the emergence of affirmative resistance, radical imagination, and a new politics of desire and dignity against authoritarian and neoliberal policies.
Plain Language Summary Cassini flew through the gap between Saturn and its rings for 22 times before plunging into the atmosphere of Saturn, ending its 20-year mission. The radio and plasma waves instrument on board Cassini helped quantify the dust hazard in this previously unexplored region. The measured density of large dust particles was much lower than expected, allowing high-value science observations during the subsequent Grand Finale orbits.
During the Ring Grazing orbits near the end of Cassini mission, the spacecraft crossed the equatorial plane near the orbit of Janus/Epimetheus (similar to 2.5 Rs). This region is populated with dust particles that can be detected by the Radio and Plasma Wave Science (RPWS) instrument via an electric field antenna signal. Analysis of the voltage waveforms recorded on the RPWS antennas provides estimations of the density and size distribution of the dust particles. Measured RPWS profiles, fitted with Lorentzian functions, are shown to be mostly consistent with the Cosmic Dust Analyzer, the dedicated dust instrument on board Cassini. The thickness of the dusty ring varies between 600 and 1,000 km. The peak location shifts north and south within 100 km of the ring plane, likely a function of the precession phase of Janus orbit.
Achieving the highest power conversion efficiencies in bulk heterojunction organic solar cells requires a morphology that delivers electron and hole percolation pathways for optimized transport, plus sufficient donor:acceptor contact area for near unity charge transfer state formation. This is a significant structural challenge, particularly in semiconducting polymer:fullerene systems. This balancing act in the model high efficiency PTB7:PC70BM blend is studied by tuning the donor:acceptor ratio, with a view to understanding the recombination loss mechanisms above and below the fullerene transport percolation threshold. The internal quantum efficiency is found to be strongly correlated to the slower carrier mobility in agreement with other recent studies. Furthermore, second-order recombination losses dominate the shape of the current density-voltage curve in efficient blend combinations, where the fullerene phase is percolated. However, below the charge transport percolation threshold, there is an electric-field dependence of first-order losses, which includes electric-field-dependent photogeneration. In the intermediate regime, the fill factor appears to be limited by both first- and second-order losses. These findings provide additional basic understanding of the interplay between the bulk heterojunction morphology and the order of recombination in organic solar cells. They also shed light on the limitations of widely used transport models below the percolation threshold.
In order to replace bio-macromolecules by stable synthetic materials in separation techniques and bioanalysis biomimetic receptors and catalysts have been developed: Functional monomers are polymerized together with the target analyte and after template removal cavities are formed in the "molecularly imprinted polymer" (MIP) which resemble the active sites of antibodies and enzymes. Starting almost 80 years ago, around 1,100 papers on MIPs were published in 2016. Electropolymerization allows to deposit MIPs directly on voltammetric electrodes or chips for quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). For the readout of MIPs for drugs amperometry, differential pulse voltammetry (DPV) and impedance spectroscopy (EIS) offer higher sensitivity as compared with QCM or SPR. Application of simple electrochemical devices allows both the reproducible preparation of MIP sensors, but also the sensitive signal generation. Electrochemical MIP-sensors for the whole arsenal of drugs, e.g. the most frequently used analgesics, antibiotics and anticancer drugs have been presented in literature and tested under laboratory conditions. These biomimetic sensors typically have measuring ranges covering the lower nano-up to millimolar concentration range and they are stable under extreme pH and in organic solvents like nonaqueous extracts.
The first molecularly imprinted polymer (MIP) for the recognition of the copper-enzyme laccase was successfully prepared by electropolymerizing scopoletin in the presence of alkaline-inactivated enzyme. Laccase-MIP and the control polymer without laccase (nonimprinted polymer, NIP) were characterized by voltammetry using the redox marker ferricyanide. After electropolymerization, the signals for ferricyanide for both the MIP and the NIP were almost completely suppressed and increased after removal of the target from the polymer layer. Rebinding of both inactivated and active laccase decreased the ferricyanide peak currents to almost equal extent. The relative decrease of signal suppression approached saturation above 10 nM. Furthermore, the surface activity of rebound laccase toward the oxidation of catechol was investigated. The surface activity approached saturation above 10 nM, a value close to the value of the measurements with ferricyanide. Interaction of NIP with laccase brought about a six times smaller signal of catechol oxidation.
Phytochemical investigation of the CH2Cl2/MeOH (1:1) extract of the roots of Lannea rivae (Chiov) Sacleux (Anacardiaceae) led to the isolation of a new alkenyl cyclohexenone derivative: (4R,6S)-4,6-dihydroxy-6-((Z)-nonadec-14′-en-1-yl)cyclohex-2-en-1-one (1), and a new alkenyl cyclohexanol derivative: (2S*,4R*,5S*)-2,4,5-trihydroxy-2-((Z)-nonadec-14′-en-1-yl)cyclohexanone (2) along with four known compounds, namely epicatechin gallate, taraxerol, taraxerone and β-sitosterol; while the stem bark afforded two known compounds, daucosterol and lupeol. Similar investigation of the roots of Lannea schweinfurthii (Engl.) Engl. led to the isolation of four known compounds: 3-((E)-nonadec-16′-enyl)phenol, 1-((E)-heptadec-14′-enyl)cyclohex-4-ene-1,3-diol, catechin, and 1-((E)-pentadec-12′-enyl)cyclohex-4-ene-1,3-diol. The structures of the isolated compounds were determined by NMR spectroscopy and mass spectrometry. The absolute configuration of compound 1 was established by quantum chemical ECD calculations. In an antibacterial activity assay using the microbroth kinetic method, compound 1 showed moderate activity against Escherichia coli while compound 2 exhibited moderate activity against Staphylococcus aureus. Compound 1 also showed moderate activity against E. coli using the disc diffusion method. The roots extract of L. rivae was notably cytotoxic against both the DU-145 prostate cancer cell line and the Vero mammalian cell line (CC50 = 5.24 and 5.20 μg/mL, respectively). Compound 1 was also strongly cytotoxic against the DU-145 cell line (CC50 = 0.55 μg/mL) but showed no observable cytotoxicity (CC50 > 100 μg/mL) against the Vero cell line. The roots extract of L. rivae and L. schweinfurthii, epicatechin gallate as well as compound 1 exhibited inhibition of carageenan-induced inflammation.
QuestionDisturbed areas offer great opportunities for restoring native biodiversity, but they are also prone to invasion by alien plants. Following the limiting similarity hypothesis, we address the question of whether or not similarity of plant functional traits helps developing seed mixtures of native communities with high resistance to invasive species at an early stage of restoration. LocationCentre of Greenhouses and Laboratories Durnast, Technische Universitat Munchen, Freising, Germany. MethodsUsing a system of linear equations, we designed native communities maximizing the similarity between the native and two invasive species according to ten functional traits. We used native grassland plants, two invasive alien species that are often problematic in disturbed areas (i.e., Ambrosia artemisiifolia and Solidago gigantea) and trait information obtained from databases. The two communities were then tested for resistance against establishment of the two invaders separately in a greenhouse experiment. We measured height of the invasive species and above-ground biomass, along with leaf area index, 4 and 8months after sowing respectively. ResultsBoth invasive species were successfully reduced by the native community designed to suppress S. gigantea dominated by small-seeded species. These results could be considered as partial support for the limiting similarity hypothesis. However, given the success of this mixture against both invasive species, suppression was better explained by a seed density effect resulting from the smaller seed mass of the native species included in this mixture. Further, the dominance of a fast-developing competitive species could also contribute to its success. ConclusionsThere was no unequivocal support for the limiting similarity hypothesis in terms of the traits selected. Instead we found that increasing seeding density of native species and selecting species with a fast vegetative development is an effective way to suppress invasive plants during early stages of restoration. If limiting similarity is used to design communities for restoration, early life-history traits should be taken into account.
Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction
(2018)
Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.
Recently, we proposed a small molecular inducing ligand strategy to assemble proteins into highly-ordered structures via dual non-covalent interactions, i.e. carbohydrate-protein interaction and dimerization of Rhodamine B. Using this approach, artificial protein microtubules were successfully constructed. In this study, we find that these microtubules exhibit a perfect CO2 responsiveness; assembly and disassembly of these microtubules were nicely controlled by the alternative passage of CO2 and N-2. Upon the injection of CO2, a negative net-charged SBA turns into a neutral or positive net-charged SBA, which elongated, to some extent, the effective distance between SBA and Rhodamine B, resulting in the disassociation of the Rhodamine B dimer. Further experimental and simulation results reveal that the CO2-responsive mechanism differs from that of solubility change of the previously reported CO2-responsive synthetic materials.
Polymeric materials possessing specific features like programmability, high deformability, and easy processability are highly desirable for creating modern actuating systems. In this study, thermoplastic shape-memory polymer actuators obtained by combining crystallizable poly(epsilon-caprolactone) (PCL) and poly(3S-isobutylmorpholin-2,5-dione) (PIBMD) segments in multiblock copolymers are described. We designed these materials according to our hypothesis that the confinement of glassy PIBMD domains present at the upper actuation temperature contribute to the stability of the actuator skeleton, especially at large programming strains. The copolymers have a phase-segregated morphology, indicated by the well-separated melting and glass transition temperatures for PIBMD and PCL, but possess a partially overlapping T-m of PCL and T-g of PIBMD in the temperature interval from 40 to 60 degrees C. Crystalline PIBMD hard domains act as strong physical netpoints in the PIBMD-PCL bulk material enabling high deformability (up to 2000%) and good elastic recoverability (up to 80% at 50 degrees C above T-m,T-PCL). In the programmed thermoplastic actuators a high content of crystallizable PCL actuation domains ensures pronounced thermoreversible shape changes upon repetitive cooling and heating. The programmed actuator skeleton, composed of PCL crystals present at the upper actuation temperature T-high and the remaining glassy PIBMD domains, enabled oriented crystallization upon cooling. The actuation performance of PIBMD-PCL could be tailored by balancing the interplay between actuation and skeleton, but also by varying the quantity of crystalline PIBMD hard domains via the copolymer composition, the applied programming strain, and the choice of T-high. The actuator with 17 mol% PIBMD showed the highest reversible elongation of 11.4% when programmed to a strain of 900% at 50 degrees C. It is anticipated that the presented thermoplastic actuator materials can be applied as modern compression textiles.
The variation of the molecular architecture of multiblock copolymers has enabled the introduction of functional behaviour and the control of key mechanical properties. In the current study, we explore the synergistic relationship of two structural components in a shape-memory material formed of a multiblock copolymer with crystallizable poly(epsilon-caprolactone) and crystallizable polyfoligo(3S-iso-butylmorpholine-2,5-dione) segments (PCL-PIBMD). The thermal and structural properties of PCL-PIBMD films were compared with PCI.-PU and PMMD-PU investigated by means of DSC, SAXS and WARS measurements. The shape-memory properties were quantified by cyclic, thermomechanical tensile tests, where deformation strains up to 900% were applied for programming PCL-PIBMD films at 50 degrees C. Toluene vapor treatment experiments demonstrated that the temporary shape was fixed mainly by glassy PIBMD domains at strains lower than 600% with the PCL contribution to fixation increasing to 42 +/- 2% at programming strains of 900% This study into the shape-memory mechanism of PCL-PIBMD provides insight into the structure function relation in multiblock copolymers with both crystallizable and glassy switching segments.
Understanding the variability of the ionosphere is important for the prediction of space weather and climate. Recent studies have shown that forcing from the lower atmosphere plays a significant role for the short-term (day-to-day) variability of the low-latitude ionosphere. The present study aims to assess the importance of atmospheric forcing for the variability of the daytime equatorial ionospheric electric field on the interannual (year-to-year) time scale. Magnetic field measurements from Huancayo (12.05 degrees S, 75.33 degrees W) are used to augment the equatorial vertical plasma drift velocity (V-Z) measurements from the Jicamarca Unattended Long-term Investigations of the Ionosphere and Atmosphere radar during 2001-2016. V-Z can be regarded as a measure of the zonal electric field. After removing the seasonal variation of similar to 10m/s, midday values of V-Z show an interannual variation of similar to 2m/s with an oscillation period of 2-3years. No evidence of solar cycle influence is found. The Ground-to-topside Atmosphere-Ionosphere model for Aeronomy, which takes into account realistic atmospheric variability below 30km, reproduces the pattern of the observed interannual variation without having to include variable forcing from the magnetosphere. The results indicate that lower atmospheric forcing plays a dominant role for the observed interannual variability of V-Z at 1200 local time.
The equatorial electrojet is an enhanced eastward current in the dayside E region ionosphere flowing along the magnetic equator. The equatorial electrojet is highly variable as it is subject to various forcing mechanisms including atmospheric waves from the lower layers of the atmosphere. There are occasionally times when the intensity of the equatorial electrojet at a fixed longitude shows an oscillatory variation with a period of approximately 6days. We present case studies of such events based on the equatorial electrojet measurements from the CHAMP and Swarm satellites. The spatial and temporal variability of the equatorial electrojet intensity during these events reveals characteristics of a westward propagating wave with zonal wavenumber 1, consistent with the effect of the quasi-6-day planetary wave. Analyses of the geopotential height data from the Aura satellite confirm the presence of the quasi-6-day planetary wave in the lower thermosphere during the events. The amplitude of the quasi-6-day variation in the equatorial electrojet intensity depends on longitude, but no systematic longitudinal dependence is found for different events. During the event of August 2010, quasi-6-day variations are also observed by ground-based magnetometers and a radar in the Peruvian sector. The effect of the quasi-6-day wave accounts for up to +/- 5.9m/s in the equatorial vertical plasma velocity at noon, which is much larger than previously predicted by a numerical model. These results suggest that the quasi-6-day planetary wave is an important source of short-term variability in the equatorial ionosphere.
Coupling land-use change and hydrologic models for quantification of catchment ecosystem services
(2018)
Representation of land-use and hydrologic interactions in respective models has traditionally been problematic. The use of static land-use in most hydrologic models or that of the use of simple hydrologic proxies in land-use change models call for more integrated approaches. The objective of this study is to assess whether dynamic feedback between land-use change and hydrology can (1) improve model performances, and/or (2) produce a more realistic quantification of ecosystem services. To test this, we coupled a land-use change model and a hydrologic mode. First, the land-use change and the hydrologic models were separately developed and calibrated. Then, the two models were dynamically coupled to exchange data at yearly time-steps. The approach is applied to a catchment in South Africa. Performance of coupled models when compared to the uncoupled models were marginal, but the coupled models excelled at the quantification of catchment ecosystem services more robustly.
Hypothesis: An effective way for fixating vesicle structures is the insertion of monomers and cross-linking agents into their bilayer, and their subsequent polymerization can lead to the formation of polymeric nanocapsules. Particularly attractive here are vesicle systems that form spontaneously well-defined small vesicles, as obtaining such small nanocapsules with sizes below 100 nm is still challenging. Experiments: A spontaneously forming well-defined vesicle system composed of the surfactants TDMAO (tetradecyldimethylamine oxide), Pluronic L35, and LiPFOS (lithium perfluorooctylsulfonate) mixture was used as template for fixation by polymerization. Therefore, styrene monomer was incorporated into the vesicle bilayer and ultimately these structures were fixated by UV induced radical polymerization. Structural alteration of the vesicles upon loading with monomer and the cross-linker as well as the effect of subsequent polymerization in the membrane were investigated in detail by turbidity measurements, dynamic and static light scattering, (DLS, SLS), and small angle neutron scattering (SANS). Findings: The analysis showed the changes on vesicle structures due to the monomer loading, and that these structures can become permanently fixed by the polymerization process. The potential of this approach to produce well-defined nanocapsules starting from a self-assembled system and following polymerization is critically evaluated. (C) 2018 Elsevier Inc. All rights reserved.
We discuss recent investigations of the interaction of polyelectrolytes with proteins. In particular, we review our recent studies on the interaction of simple proteins such as human serum albumin (HSA) and lysozyme with linear polyelectrolytes, charged dendrimers, charged networks, and polyelectrolyte brushes. In all cases discussed here, we combined experimental work with molecular dynamics (MD) simulations and mean-field theories. In particular, isothermal titration calorimetry (ITC) has been employed to obtain the respective binding constants K-b and the Gibbs free energy of binding. MD simulations with explicit counterions but implicit water demonstrate that counterion release is the main driving force for the binding of proteins to strongly charged polyelectrolytes: patches of positive charges located on the surface of the protein become multivalent counterions of the polyelectrolyte, thereby releasing a number of counterions condensed on the polyelectrolyte. The binding Gibbs free energy due to counterion release is predicted to scale with the logarithm of the salt concentration in the system, which is verified by both simulations and experiment. In several cases, namely, for the interaction of proteins with linear polyelectrolytes and highly charged hydrophilic dendrimers, the binding constant could be calculated from simulations to very good approximation. This finding demonstrated that in these cases explicit hydration effects do not contribute to the Gibbs free energy of binding. The Gibbs free energy can also be used to predict the kinetics of protein uptake by microgels for a given system by applying dynamic density functional theory. The entire discussion demonstrates that the direct comparison of theory with experiments can lead to a full understanding of the interaction of proteins with charged polymers. Possible implications for applications, such as drug design, are discussed.
Vibrationally resolved lowest-energy bands of the photoelectron spectra (PES) of adamantane, diamantane, and urotropine were simulated by a time-dependent correlation function approach within the harmonic approximation. Geometries and normal modes for neutral and cationic molecules were obtained from B3LYP hybrid density functional theory (DFT). It is shown that the simulated spectra reproduce the experimentally observed vibrational finestructure (or its absence) quite well. Origins of the finestructure are discussed and related to recurrences of autocorrelation functions and dominant vibrations. Remaining quantitative and qualitative errors of the DFT-derived PES spectra refer to (i) an overall redshift by ∼0.5 eV and (ii) the absence of satellites in the high-energy region of the spectra. The former error is shown to be due to the neglect of many-body corrections to ordinary Kohn-Sham methods, while the latter has been argued to be due to electron-nuclear couplings beyond the Born-Oppenheimer approximation [Gali et al., Nat. Commun. 7, 11327 (2016)].
Vibrationally resolved absorption and emission (fluorescence) spectra of perylene and its N-derivatives in gas phase and in solution (acetonitrile) were simulated using a time-dependent approach based on correlation functions determined by density functional theory. By systematically varying the number and position of N atoms, it is shown that the presence of nitrogen heteroatoms has a negligible effect on the molecular structure and geometric distortions upon electronic transitions, while spectral properties change: in particular the number of N atoms is important while their position is less decisive. Thus, the N-substitution can be used to fine-tune the optical properties of perylene-based molecules.
Fragmentation of endohedral fullerene Ho3N@C-80 in an intense femtosecond near-infrared laser field
(2018)
The fragmentation of gas phase endohedral fullerene, Ho3N@C-80, was investigated using femtosecond near-infrared laser pulses with an ion velocity map imaging spectrometer. We observed that Ho+ abundance associated with carbon cage opening dominates at an intensity of 1.1 x 10(14) W/cm(2). As the intensity increases, the Ho+ yield associated with multifragmentation of the carbon cage exceeds the prominence of Ho+ associated with the gentler carbon cage opening. Moreover, the power law dependence of Ho+ on laser intensity indicates that the transition of the most likely fragmentation mechanisms occurs around 2.0 x 10(14) W/cm(2).
By using 3-year global positioning system (GPS) measurements from December 2013 to November 2016, we provide in this study a detailed survey on the climatology of the GPS signal loss of Swarm onboard receivers. Our results show that the GPS signal losses prefer to occur at both low latitudes between +/- 5 and +/- 20 degrees magnetic latitude (MLAT) and high latitudes above 60 degrees MLAT in both hemispheres. These events at all latitudes are observed mainly during equinoxes and December solstice months, while totally absent during June solstice months. At low latitudes the GPS signal losses are caused by the equatorial plasma irregularities shortly after sunset, and at high latitude they are also highly related to the large density gradients associated with ionospheric irregularities. Additionally, the high-latitude events are more often observed in the Southern Hemisphere, occurring mainly at the cusp region and along nightside auroral latitudes. The signal losses mainly happen for those GPS rays with elevation angles less than 20 degrees, and more commonly occur when the line of sight between GPS and Swarm satellites is aligned with the shell structure of plasma irregularities. Our results also confirm that the capability of the Swarm receiver has been improved after the bandwidth of the phase-locked loop (PLL) widened, but the updates cannot radically avoid the interruption in tracking GPS satellites caused by the ionospheric plasma irregularities. Additionally, after the PLL bandwidth increased larger than 0.5 Hz, some unexpected signal losses are observed even at middle latitudes, which are not related to the ionospheric plasma irregularities. Our results suggest that rather than 1.0 Hz, a PLL bandwidth of 0.5 Hz is a more suitable value for the Swarm receiver.
Transdualism
(2018)
The author introduces the concept of transdualism to critique dualism without relying on a dualistic model of critique, the modus operandi necessary for a critique against sexual dualism and hetero/cisnormativity. Transdualism offers an opportunity to dwell within that operation by staying below (not beyond) the “dualism,” that is, below the logic of either/or. The essay will explore the notion of “transdualism” through the hexagram Tai of the Yi Jing, which is often used in medical contexts to illustrate the body-of-orifices of Huangdi Neijing or the Inner Canon of the Yellow Emperor. The author reads this body-of-orifices, which is primarily represented by its nine major bodily tunnels, with yinyang philosophy as gender/sex indeterminant and shows that the Inner Canon's yinyang body-of-orifices points to something more transgressive, which could unsettle from within the naturalism of gender and sexual dualism and the nature/culture as well as other dualistic divides that have informed contemporary critical rethinking of embodiment. By unpacking the hexagram Tai alongside Inner Canon's body-of-orifices. as well as contemporary feminist, queer, and transgender theorizations of the body and sexuality, this essay aims at rethinking the materio-discursive complexity of the body-of-orifices, which has been either dualistically separated into antagonisms between man and woman, sex and gender, body and discourse, yin and yang; or one-sidedly reduced to a function of “social construction,” knowable only through language—or problematically lumped together in a gender-is-fluid postmodern “both-and,” which supposedly overcomes the metaphysico-theological “either/or.”
The central Andes
(2018)
The Central Andes and the Atacama Desert represent a unique geological, climatic, and magmatic setting on our planet. It is the only place on Earth where subduction of an oceanic plate below an active continental margin has led to an extensive mountain chain and an orogenic plateau that is second in size only to the Tibetan Plateau, which resulted from continental collision. In this article, we introduce the history of the Central Andes and the evolution of its landscape. We also discuss links between tectonic forces, magmatism, and the extreme hyperarid climate of this land that, in turn, has led to rich deposits of precious ores and minerals.
Present-day domestic horses are immensely diverse in their maternally inherited mitochondrial DNA, yet they show very little variation on their paternally inherited Y chromosome. Although it has recently been shown that Y chromosomal diversity in domestic horses was higher at least until the Iron Age, when and why this diversity disappeared remain controversial questions. We genotyped 16 recently discovered Y chromosomal single-nucleotide polymorphisms in 96 ancient Eurasian stallions spanning the early domestication stages (Copper and Bronze Age) to the Middle Ages. Using this Y chromosomal time series, which covers nearly the entire history of horse domestication, we reveal how Y chromosomal diversity changed over time. Our results also show that the lack of multiple stallion lineages in the extant domestic population is caused by neither a founder effect nor random demographic effects but instead is the result of artificial selection-initially during the Iron Age by nomadic people from the Eurasian steppes and later during the Roman period. Moreover, the modern domestic haplotype probably derived from another, already advantageous, haplotype, most likely after the beginning of the domestication. In line with recent findings indicating that the Przewalski and domestic horse lineages remained connected by gene flow after they diverged about 45,000 years ago, we present evidence for Y chromosomal introgression of Przewalski horses into the gene pool of European domestic horses at least until medieval times.
Cobras are among the most widely known venomous snakes, and yet their taxonomy remains incompletely understood, particularly in Africa. Here, we use a combination of mitochondrial and nuclear gene sequences and morphological data to diagnose species limits within the African forest cobra, Naja (Boulengerina) melanoleuca. Mitochondrial DNA sequences reveal deep divergences within this taxon. Congruent patterns of variation in mtDNA, nuclear genes and morphology support the recognition of five separate species, confirming the species status of N. subfulva and N. peroescobari, and revealing two previously unnamed West African species, which are described as new: Naja (Boulengerina) guineensis sp. nov. Broadley, Trape, Chirio, Ineich & Wuster, from the Upper Guinea forest of West Africa, and Naja (Boulengerina) savannula sp. nov. Broadley, Trape, Chirio & Wuster, a banded form from the savanna-forest mosaic of the Guinea and Sudanian savannas of West Africa. The discovery of cryptic diversity in this iconic group highlights our limited understanding of tropical African biodiversity, hindering our ability to conserve it effectively.
Dumortierite was synthesized in piston-cylinder experiments at 2.5-4.0 GPa, 650-700 degrees C in the Al2O3 -B2O3-SiO2-H2O (ABSH) system. Electron-microprobe (EMP) analyses reveal significant boron-excess (up to 0.26 B-[4] per formula unit, pfu) and silicon-deficiency relative to the ideal anhydrous dumortierite stoichiometry Al7BSi3O18 . The EMP data in conjunction with results from single-crystal Raman spectroscopy and powder X-ray diffraction provide evidence that silicon at the tetrahedral site is replaced by excess boron via the substitution Si-[4] <--> B-[4] + H. The Raman spectrum of synthetic dumortierite in the frequency region 2000 4000 cm(-1) comprises eight bands, of which six are located at frequencies below 3400 cm(-1). This points to strong hydrogen bonding, most likely O2-H center dot center dot center dot O7 and O7-H center dot center dot center dot O2, arising from a high number of octahedral vacancies at the All site and substitution of trivalent Al3+ and B3+ for Si4+ at Si1 and Si2 sites, causing decreasing acceptor-donor distances and lower incident valence at the acceptor oxygen. Contrary to the synthetic high-pressure ABSH-dumortierite, magnesiodumortierite from the Dora-Maira Massif, which is assumed to have formed at similar conditions (2.5-3.0 GPa, 700 degrees C), does not show any B-excess. Tourmaline shows an analogous behaviour in that magnesium-rich (e.g., dravitic) tourmaline formed at high pressure shows no or only minor amounts of tetrahedral boron, whereas natural aluminum-rich tourmaline and synthetic olenitic tourmaline formed at high pressures can incorporate significant amounts of tetrahedral boron. Two mechanisms might account for this discrepancy: (i) Structural avoidance of Mg-[6]-(OR3+)-R-[4] configurations in magnesiodumortierite due to charge deficieny at the oxygens O2 and O7 and strong local distortion of M1 due to decreased O2-O7 bond length, and/or (ii) decreasing fluid mobility of boron in Al-rich systems at high pressures.
Aims Anterior lumbar interbody fusion procedures (ALIF) and total disc replacement (TDR) with anterior exposure of the lumbar spine entail a risk of a vascular injury and dysfunction of the sympathetic and parasympathetic nerves due to disturbance of the inferior and superior hypogastric plexus. While retrograde ejaculation is a known complication of the anterior spinal approach in males, post-operative sexual as well as urinary function in females has not yet been thoroughly investigated and was hence the aim of this study. Methods Fifteen female patients documented their sexual and urinary function preoperatively, 3 months and 6 months postoperatively, using the validated questionnaires FSFI (Female Sexual Function Index) and ICIQ (International Consultation of Incontinence Questionnaire). Randomization tests were used to statistically analyze expectation values over time (two-sided, P < 0.05). Results While no statistically significant change in the total FSFI score occurred over time, a significant increase in FSFI desire score was noted between preoperative (2.95 +/- 0.8) and 6 months follow-up (3.51 +/- 0.6, P = 0.02). Urinary continence remained unchanged over time. Conclusion In summary, ALIF and lumbar TDR do not seem to negatively influence sexual and urinary function in females. In contrast, increased sexual desire was noted, likely secondary to post-surgical pain relief.
While the role of and consequences of being a bystander to face-to-face bullying has received some attention in the literature, to date, little is known about the effects of being a bystander to cyberbullying. It is also unknown how empathy might impact the negative consequences associated with being a bystander of cyberbullying. The present study focused on examining the longitudinal association between bystander of cyberbullying depression, and anxiety, and the moderating role of empathy in the relationship between bystander of cyberbullying and subsequent depression and anxiety. There were 1,090 adolescents (M-age = 12.19; 50% female) from the United States included at Time 1, and they completed questionnaires on empathy, cyberbullying roles (bystander, perpetrator, victim), depression, and anxiety. One year later, at Time 2, 1,067 adolescents (M-age = 13.76; 51% female) completed questionnaires on depression and anxiety. Results revealed a positive association between bystander of cyberbullying and depression and anxiety. Further, empathy moderated the positive relationship between bystander of cyberbullying and depression, but not for anxiety. Implications for intervention and prevention programs are discussed.
The current study was designed to assess early adolescents’ response evaluation and decision for hypothetical peer victimization vignettes. Participants were 336 (59% girls; X¯¯¯ age = 12.55) seventh and eighth graders from one school in the Midwestern United States. Adolescents read a hypothetical online or offline social situation and answered questions designed to access internal congruence, response evaluation, response efficacy, emotional outcome expectancy, and social outcome expectancy. Girls were more likely to believe that aggressive responses online and offline would lead to positive social and emotional outcome expectancies when compared with boys. Adolescents were more likely to believe that offline and online aggressive responses were legitimate responses to face-to-face victimization, feel that aggressive responses online or offline were easier to execute in response to face-to-face victimization, and that aggressive responses online or offline would lead to positive emotions and better social outcomes.
Flowers represent a key innovation during plant evolution. Driven by reproductive optimization, evolution of flower morphology has been central in boosting species diversification. In most cases, this has happened through specialized interactions with animal pollinators and subsequent reduction of gene flow between specialized morphs. While radiation has led to an enormous variability in flower forms and sizes, recurrent evolutionary patterns can be observed. Here, we discuss the targets of selection involved in major trends of pollinator-driven flower evolution. We review recent findings on their adaptive values, developmental grounds and genetic bases, in an attempt to better understand the repeated nature of pollinator-driven flower evolution. This analysis highlights how structural innovation can provide flexibility in phenotypic evolution, adaptation and speciation. (C) 2017 Elsevier Ltd. All rights reserved.
Nitraria is a halophytic taxon (i.e., adapted to saline environments) that belongs to the plant family Nitrariaceae and is distributed from the Mediterranean, across Asia into the south-eastern tip of Australia. This taxon is thought to have originated in Asia during the Paleogene (66-23 Ma), alongside the proto-Paratethys epicontinental sea. The evolutionary history of Nitraria might hold important clues on the links between climatic and biotic evolution but limited taxonomic documentation of this taxon has thus far hindered this line of research. Here we investigate if the pollen morphology and the chemical composition of the pollen wall are informative of the evolutionary history of Nitraria and could explain if origination along the proto-Paratethys and dispersal to the Tibetan Plateau was simultaneous or a secondary process. To answer these questions, we applied a novel approach consisting of a combination of Fourier Transform Infrared spectroscopy (FTIR), to determine the chemical composition of the pollen wall, and pollen morphological analyses using Light Microscopy (LM) and Scanning Electron Microscopy (SEM). We analysed our data using ordinations (principal components analysis and non-metric multidimensional scaling), and directly mapped it on the Nitrariaceae phylogeny to produce a phylomorphospace and a phylochemospace. Our LM, SEM and FTIR analyses show clear morphological and chemical differences between the sister groups Peganum and Nitraria. Differences in the morphological and chemical characteristics of highland species (Nitraria schoberi, N. sphaerocarpa, N. sibirica and N. tangutorum) and lowland species (Nitraria billardierei and N. retusa) are very subtle, with phylogenetic history appearing to be a more important control on Nitraria pollen than local environmental conditions. Our approach shows a compelling consistency between the chemical and morphological characteristics of the eight studied Nitrariaceae species, and these traits are in agreement with the phylogenetic tree. Taken together, this demonstrates how novel methods for studying fossil pollen can facilitate the evolutionary investigation of living and extinct taxa, and the environments they represent.
At Saturn electrons are trapped in the planet’s magnetic field and accelerated to relativistic energies to form the radiation belts, but how this dramatic increase in electron energy occurs is still unknown. Until now the mechanism of radial diffusion has been assumed but we show here that in-situ acceleration through wave particle interactions, which initial studies dismissed as ineffectual at Saturn, is in fact a vital part of the energetic particle dynamics there. We present evidence from numerical simulations based on Cassini spacecraft data that a particular plasma wave, known as Z-mode, accelerates electrons to MeV energies inside 4 RS (1 RS = 60,330 km) through a Doppler shifted cyclotron resonant interaction. Our results show that the Z-mode waves observed are not oblique as previously assumed and are much better accelerators than O-mode waves, resulting in an electron energy spectrum that closely approaches observed values without any transport effects included.
Ice-wedge polygons are widespread periglacial features and influence landscape hydrology and carbon storage. The influence of climate and topography on polygon development is not entirely clear, however, giving high uncertainties to projections of permafrost development. We studied the mid- to late Holocene development of modern ice-wedge polygon sites to explore drivers of change and reasons for long-term stability. We analyzed organic carbon, total nitrogen, stable carbon isotopes, grain size composition and plant macrofossils in six cores from three polygons. We found that ail sites developed from aquatic to wetland conditions. In the mid-Holocene, shallow lakes and partly submerged ice-wedge polygons existed at the studied sites. An erosional hiatus of ca 5000 years followed, and ice-wedge polygons re-initiated within the last millennium. Ice-wedge melt and surface drying during the last century were linked to climatic warming. The influence of climate on ice-wedge polygon development was outweighed by geomorphology during most of the late Holocene. Recent warming, however, caused ice-wedge degradation at all sites. Our study showed that where waterlogged ground was maintained, low-centered polygons persisted for millennia. Ice-wedge melt and increased drainage through geomorphic disturbance, however, triggered conversion into high-centered polygons and may lead to self-enhancing degradation under continued warming.
Full water splitting into hydrogen and oxygen on semiconductor nanocrystals is a challenging task; overpotentials must be overcome for both half-reactions and different catalytic sites are needed to facilitate them. Additionally, efficient charge separation and prevention of back reactions are necessary. Here, we report simultaneous H-2 and O-2 evolution by CdS nanorods decorated with nanoparticulate reduction and molecular oxidation co-catalysts. The process proceeds entirely without sacrificial agents and relies on the nanorod morphology of CdS to spatially separate the reduction and oxidation sites. Hydrogen is generated on Pt nanoparticles grown at the nanorod tips, while Ru(tpy)(bpy)Cl-2-based oxidation catalysts are anchored through dithiocarbamate bonds onto the sides of the nanorod. O-2 generation from water was verified by O-18 isotope labelling experiments, and time-resolved spectroscopic results confirmed efficient charge separation and ultrafast electron and hole transfer to the reaction sites. The system demonstrates that combining nanoparticulate and molecular catalysts on anisotropic nanocrystals provides an effective pathway for visible-light-driven photocatalytic water splitting.
Background:
Mother-infant interaction provides important training for the infant’s ability to cope with stress and the development of resilience. Prenatal stress (PS) and its impact on the offspring’s development have long been a focus of stress research, with studies highlighting both harmful and beneficial effects. The aim of the current study was to examine the possible influence of both psychological stress and hypothalamic-pituitary-adrenal (HPA) axis activity during pregnancy with mother-child dyadic behavior following stress exposure.
Methods:
The behavior of 164 mother-infant dyads during the still-face situation was filmed at six months postpartum and coded into three dyadic patterns: 1) both positive, 2) infant protesting-mother positive, and 3) infant protesting-mother negative. PS exposure was assessed prenatally according to psychological measures (i.e., psychopathological, perceived and psychosocial PS; n = 164) and HPA axis activity measures (maternal salivary cortisol, i.e., cortisol decline and area under the curve with respect to ground (AUCg); n = 134).
Results:
Mother-infant dyads in both the high- and low-stress groups showed decreasing positive and increasing negative dyadic behavior in the reunion episode, which is associated with the well-known “still-face” and “carry-over” effect. Furthermore, mother-infant dyads with higher psychosocial PS exhibited significantly more positive dyadic behavior than the low psychosocial PS group in the first play episode, but not in the reunion episode. Similarly, mother-infant dyads with high HPA axis activity (i.e. high AUCg) but steeper diurnal cortisol decline (i.e. cortisol decline) displayed significantly less negative behavior in the reunion episode than dyads with low HPA axis activity. No significant results were found for psychopathological stress and perceived stress.
Conclusions:
The results suggest a beneficial effect of higher psychosocial PS and higher prenatal maternal HPA axis activity in late gestation, which is in line with “stress inoculation” theories.
Anne-Katrin Wolf beschäftigt sich mit der Aktivlegitimation im Individualbeschwerdeverfahren der UN-Menschenrechtskonventionen. Sie gibt einerseits eine leitfadenartige Übersicht zum Zulässigkeitskriterium der Aktivlegitimation. Andererseits zeigt sie, dass die Auslegungspraxis der UN-Ausschüsse zu dessen Voraussetzungen derzeit an einigen Stellen zu eng gefasst ist, um einen effektiven Menschenrechtsschutz zu gewährleisten. Im Zentrum steht dabei die Kategorisierung der UN-Menschenrechtskonventionen anhand der jeweiligen Regelungsmaterie und die daran anknüpfende, unterschiedlich weit reichenden Beschwerdemöglichkeiten von Individuen und Kollektiven wie Verbänden oder Nichtregierungsorganisationen. Sofern eine Ausgestaltung durch die Ausschüsse selbst noch nicht erfolgt ist oder die Autorin bisher angewendeten Kriterien als defizitär bewertet, entwickelt sie Vorschläge zu einer möglichen Ausformung des Kriteriums der Aktivlegitimation in der Zusammenschau mit dem jeweiligen Schutzgehalt der Konvention.
Proglacial environments are ideal for studying the development of soils through the changes of rocks exposed by glacier retreat to weathering and microbial processes. Carbon (C) and nitrogen (N) contents as well as soil pH and soil elemental compositions are thought to be dominant factors structuring the bacterial, archaeal and fungal communities in the early stages of soil ecosystem formation. However, the functional linkages between C and N contents, soil composition and microbial community structures remain poorly understood. Here, we describe a multivariate analysis of geochemical properties and associated microbial community structures between a moraine and a glaciofluvial outwash in the proglacial area of a High Arctic glacier (Longyearbreen, Svalbard). Our results reveal distinct differences in developmental stages and heterogeneity between the moraine and the glaciofluvial outwash. We observed significant relationships between C and N contents, delta C-13(org) and delta N-15 isotopic ratios, weathering and microbial abundance and community structures. We suggest that the observed differences in microbial and geochemical parameters between the moraine and the glaciofluvial outwash are primarily a result of geomorphological variations of the proglacial terrain.
In public perception, abnormal animal behavior is widely assumed to be a potential earthquake precursor, in strong contrast to the viewpoint in natural sciences. Proponents of earthquake prediction via animals claim that animals feel and react abnormally to small changes in environmental and physico-chemical parameters related to the earthquake preparation process. In seismology, however, observational evidence for changes of physical parameters before earthquakes is very weak. In this study, we reviewed 180 publications regarding abnormal animal behavior before earthquakes and analyze and discuss them with respect to (1) magnitude-distance relations, (2) foreshock activity, and (3) the quality and length of the published observations. More than 700 records of claimed animal precursors related to 160 earthquakes are reviewed with unusual behavior of more than 130 species. The precursor time ranges from months to seconds prior to the earthquakes, and the distances from a few to hundreds of kilometers. However, only 14 time series were published, whereas all other records are single observations. The time series are often short (the longest is 1 yr), or only small excerpts of the full data set are shown. The probability density of foreshocks and the occurrence of animal precursors are strikingly similar, suggesting that at least parts of the reported animal precursors are in fact related to foreshocks. Another major difficulty for a systematic and statistical analysis is the high diversity of data, which are often only anecdotal and retrospective. The study clearly demonstrates strong weaknesses or even deficits in many of the published reports on possible abnormal animal behavior. To improve the research on precursors, we suggest a scheme of yes and no questions to be assessed to ensure the quality of such claims.
Background: Cigarette smoking has severe adverse health consequences in adults and in the offspring of mothers who smoke during pregnancy. One of the most widely reported effects of smoking during pregnancy is reduced birth weight which is in turn associated with chronic disease in adulthood. Epigenome-wide association studies have revealed that smokers show a characteristic "smoking methylation pattern", and recent authors have proposed that DNA methylation mediates the impact of maternal smoking on birth weight. The aims of the present study were to replicate previous reports that methylation mediates the effect of maternal smoking on birth weight, and for the first time to investigate whether the observed mediation effects are sex-specific in order to account for known sex-specific differences in methylation levels. Methods: Methylation levels in the cord blood of 313 newborns were determined using the Illumina HumanMethylation450K Beadchip. A total of 5,527 CpG sites selected on the basis of evidence from the literature were tested. To determine whether the observed association between maternal smoking and birth weight was attributable to methylation, mediation analyses were performed for significant CpG sites. Separate analyses were then performed in males and females. Results: Following quality control, 282 newborns eventually remained in the analysis. A total of 25 mothers had smoked consistently throughout the pregnancy. The birthweigt of newborns whose mothers had smoked throughout pregnancy was reduced by >200g. After correction for multiple testing, 30 CpGs showed differential methylation in the maternal smoking subgroup including top "smoking methylation pattern" genes AHRR, MYO1G, GFI1, CYP1A1, and CNTNAP2. The effect of maternal smoking on birth weight was partly mediated by the methylation of cg25325512 (PIM1); cg25949550 (CNTNAP2); and cg08699196 (ITGB7). Sex-specific analyses revealed a mediating effect for cg25949550 (CNTNAP2) in male newborns. Conclusion: The present data replicate previous findings that methylation can mediate the effect of maternal smoking on birth weight. The analysis of sex-dependent mediation effects suggests that the sex of the newborn may have an influence. Larger studies are warranted to investigate the role of both the identified differentially methylated loci and the sex of the newborn in mediating the association between maternal smoking during pregnancy and birth weight.
Galaxies are surrounded by large reservoirs of gas, mostly hydrogen, that are fed by inflows from the intergalactic medium and by outflows from galactic winds. Absorption-line measurements along the lines of sight to bright and rare background quasars indicate that this circumgalactic medium extends far beyond the starlight seen in galaxies, but very little is known about its spatial distribution. The Lyman-alpha transition of atomic hydrogen at a wavelength of 121.6 nanometres is an important tracer of warm (about 104 kelvin) gas in and around galaxies, especially at cosmological redshifts greater than about 1.6 at which the spectral line becomes observable from the ground. Tracing cosmic hydrogen through its Lyman-a emission has been a long-standing goal of observational astrophysics(1-3), but the extremely low surface brightness of the spatially extended emission is a formidable obstacle. A new window into circumgalactic environments was recently opened by the discovery of ubiquitous extended Lyman-alpha emission from hydrogen around high-redshift galaxies(4,5). Such measurements were previously limited to especially favourable systems(6-8) or to the use of massive statistical averaging(9,10) because of the faintness of this emission. Here we report observations of low-surface-brightness Lyman-alpha emission surrounding faint galaxies at redshifts between 3 and 6. We find that the projected sky coverage approaches 100 per cent. The corresponding rate of incidence (the mean number of Lyman-alpha emitters penetrated by any arbitrary line of sight) is well above unity and similar to the incidence rate of high-column-density absorbers frequently detected in the spectra of distant quasars(11-14). This similarity suggests that most circumgalactic atomic hydrogen at these redshifts has now been detected in emission.
Enzymes have recently attracted increasing attention in material research based on their capacity to catalyze the conversion of polymer-bound moieties for synthesizing polymer networks, particularly bulk hydrogels. hi this study. the surface immobilization of a relevant enzyme. mushroom tyrosinase, should be explored using glass as model surface. In a first step. the glass support was functionalized with silanes to introduce either amine or carboxyl groups, as confirmed e.g. by X-ray photoelectron spectroscopy. By applying glutaraldehyde and EDC/NHS chemistry, respectively, surfaces have been activated for subsequent successful coupling of tyrosinase. Via protein hydrolysis and amino acid characterization by HPLC, the quantity of bound tyrosinase was shown to correspond to a full surface coverage. Based on the visualized enzymatic conversion of a test substrate at the glass support. the functionalized surfaces may be explored for surface-associated material synthesis in the future.
Background
Biomarker-based analyses are commonly reported in observational epidemiological studies; however currently there are no specific study quality assessment tools to assist evaluation of conducted research. Accounting for study design and biomarker measurement would be important for deriving valid conclusions when conducting systematic data evaluation.
Methods
We developed a study quality assessment tool designed specifically to assess biomarker-based cross-sectional studies (BIOCROSS) and evaluated its inter-rater reliability. The tool includes 10-items covering 5 domains: ‘Study rational’, ‘Design/Methods’, ‘Data analysis’, ‘Data interpretation’ and ‘Biomarker measurement’, aiming to assess different quality features of biomarker cross-sectional studies. To evaluate the inter-rater reliability, 30 studies were distributed among 5 raters and intraclass correlation coefficients (ICC-s) were derived from respective ratings.
Results
The estimated overall ICC between the 5 raters was 0.57 (95% Confidence Interval (CI): 0.38–0.74) indicating a good inter-rater reliability. The ICC-s ranged from 0.11 (95% CI: 0.01–0.27) for the domain ‘Study rational’ to 0.56 (95% CI: 0.40–0.72) for the domain ‘Data interpretation’.
Conclusion
BIOCROSS is a new study quality assessment tool suitable for evaluation of reporting quality from cross-sectional epidemiological studies employing biomarker data. The tool proved to be reliable for use by biomedical scientists with diverse backgrounds and could facilitate comprehensive review of biomarker studies in human research.
Previous research found that memory is not only better for emotional information but also for neutral information that has been encoded in the context of an emotional event. In the present ERP study, we investigated two factors that may influence memory for neutral and emotional items: temporal proximity between emotional and neutral items during encoding, and retention interval (immediate vs. delayed). Forty-nine female participants incidentally encoded 36 unpleasant and 108 neutral pictures (36 neutral pictures preceded an unpleasant picture, 36 followed an unpleasant picture, and 36 neutral pictures were preceded and followed by neutral pictures) and participated in a recognition memory task either immediately (N=24) or 1 week (N=25) after encoding. Results showed better memory for emotional pictures relative to neutral pictures. In accordance, enhanced centroparietal old/new differences (500-900 ms) during recognition were observed for unpleasant compared to neutral pictures, most pronounced for the 1-week interval. Picture position effects, however, were only subtle. During encoding, late positive potentials for neutral pictures were slightly lower for neutral pictures following unpleasant ones, but only at trend level. To summarize, we could replicate and extend previous ERP findings showing that emotionally arousing events are better recollected than neutral events, particularly when memory is tested after longer retention intervals. Picture position during encoding, however, had only small effects on elaborative processing and no effects on memory retrieval.
The genesis of chronic pain is explained by a biopsychosocial model. It hypothesizes an interdependency between environmental and genetic factors provoking aberrant long-term changes in biological and psychological regulatory systems. Physiological effects of psychological and physical stressors may play a crucial role in these maladaptive processes. Specifically, long-term demands on the stress response system may moderate central pain processing and influence descending serotonergic and noradrenergic signals from the brainstem, regulating nociceptive processing at the spinal level. However, the underlying mechanisms of this pathophysiological interplay still remain unclear. This paper aims to shed light on possible pathways between physical (exercise) and psychological stress and the potential neurobiological consequences in the genesis and treatment of chronic pain, highlighting evolving concepts and promising research directions in the treatment of chronic pain. Two treatment forms (exercise and mindfulness-based stress reduction as exemplary therapies), their interaction, and the dose-response will be discussed in more detail, which might pave the way to a better understanding of alterations in the pain matrix and help to develop future prevention and therapeutic concepts
The impact of reservoir heterogeneities on High-Temperature aquifer thermal energy storage systems
(2018)
We conducted a geoscientific feasibility study for the development of a high-temperature thermal aquifer energy storage system (HT-ATES) outside the capital of Muscat, northern Oman. The aquifer storage is part of a solar geothermal cooling project for the sustainable and continuous cooling of office buildings. The main concept is that excess solar energy will be stored in the subsurface through hot water injection and subsequently utilised as auxiliary energy source during peak demand times. The characterisation of aquifer heterogeneities is thus essential to predict subsurface thermal heat plume development and recovery efficiency of the storage system. We considered two aquifer systems as potential storage horizons, (i) a clastic-dominated alluvial fan system where individual channel systems in combination with diagenetic alterations constitute the main heterogeneities and (ii) a carbonate-dominated system represented by a homogenous layer-cake architecture. The feasibility study included a multidisciplinary approach from initial field work, geocellular reservoir modelling to finite element fluid flow and thermal modelling. Our results show that for the HT-ATES system, with a high frequency of injection and production cycles, heat loss mainly occurs due to heterogeneities in the permeability field of the aquifer in combination with buoyancy driven vertical fluid flow. An impermeable cap-rock is needed to keep the heat plume in place. Conductive heat loss is a minor issue. Highly complex heat plume geometries are apparent in the clastic channel system and ATES well planning is challenging due to the complex and interconnected high permeable channels. The carbonate sequence shows uniform plume geometries due to the layer cake architecture of the system and is tentatively more suitable for ATES development. Based on our findings we propose the general concept of HT-ATES traps, incorporating and building on expertise and knowledge from petroleum and reservoir geology regarding reservoir rocks and suitable trap&seal geometries. The concept can be used as guideline for future high-temperature aquifer storage exploration and development.
Ab 1806 versuchte Napoleon über sieben Jahre hinweg, den europäischen Kontinent gegen jegliche Importe aus Großbritannien abzuschotten. Dieses protektionistische Großexperiment löste in der zeitgenössischen Presse intensive Debatten zu wirtschaftstheoretischen Fragen aus: Fördert ökonomischer Isolationismus den nationalen Wohlstand? Können internationale Rechtsregelungen einem Handelskrieg entgegenwirken? Oder werden nationaler Wohlstand und damit globaler Frieden nicht eher durch allgemeinen Freihandel begünstigt? Alix Winter stellt das wirtschaftspolitische Ereignis der Kontinentalsperre als Kristallisationspunkt öffentlicher Auseinandersetzungen über ökonomische Grundsatzfragen heraus und identifiziert das frühe 19. Jahrhundert als Radikalisierungsphase aufklärerischer liberaler Wirtschaftstheorien.In 1806, Napoleon attempted to seal off the entire European continent from British imports. This ambitious protectionist experiment set off extensive debates about questions of economic theory. Did economic isolation foster the wealth of nations? Could international law prevent the outbreak of a maritime trade war? Or would global free trade promote wealth and peace among all nations? In this book, Alix Winter studies how the continental system served as a focal point for public discussions about fundamental economical questions and how the early nineteenth century witnessed the radicalisation of Enlightenment liberal economic theories.
Dass sich die repräsentative Demokratie in Deutschland im Wandel befindet, ist nicht neu und kaum umstritten. Herausforderungen im Kontext der Partizipation und Repräsentation rufen ihrerseits Probleme auf Seiten der Input-Legitimation hervor. Demgemäß ist das grundlegende demokratiepolitische Anliegen dieser Arbeit, am Beispiel der Bundes- und Berliner Landesebene darzustellen, wie der repräsentative Politikprozess partizipativer und dennoch effektiv gestaltet werden kann. Basierend auf der philosophischen Strömung des Pragmatismus verfolgt und diskutiert die Arbeit die Synthese aus der pragmatistischen Demokratiekonzeption von Archon Fung und dem empirischen Forschungsprogramm der kriterienbasierten Evaluation demokratischer Innovationen. Dabei wird das analytische Vorgehen Archon Fungs kritisch erweitert, um dem dieser Arbeit zugrunde liegenden Konzept einer komplexen Bürgergesellschaft – als normativer und praktischer Bezugspunkt – gerecht zu werden. Fungs Konzept wird demnach um die liberale Sphäre der Öffentlichkeit, mithin um die zivilgesellschaftlichen Handlungszusammenhänge ergänzt. Auf Grundlage der Diskussion von demokratischen Innovationen werden schließlich demokratie- und engagementpolitische Handlungsempfehlungen in der Dimension der Partizipation und in der Dimension der Repräsentation formuliert. Mithin verfolgt die Arbeit eine problem- und lösungsorientierte Ergänzung der repräsentativen Demokratie. Gleichwohl ist die Arbeit als eine pragmatistisch angeleitete Konzeptstudie für die Entwicklung einer beteiligungsorientierten Praxis in der repräsentativen Demokratie zu verstehen, die trotz ihres theoretischen Charakters ganz im Sinne des Pragmatismus die notwendige empirische Orientierung aufweist. Damit wird das zuweilen problematische Verhältnis zwischen Politischer Theorie und empirischer Demokratieforschung überwunden.
Increasing Earth’s surface air temperature yields an intensification of its hydrological cycle. As a consequence, the risk of river floods will increase regionally within the next two decades due to the atmospheric warming caused by past anthropogenic greenhouse gas emissions. The direct economic losses caused by these floods can yield regionally heterogeneous losses and gains by propagation within the global trade and supply network. Here we show that, in the absence of large-scale structural adaptation, the total economic losses due to fluvial floods will increase in the next 20 years globally by 17% despite partial compensation through market adjustment within the global trade network. China will suffer the strongest direct losses, with an increase of 82%. The United States is mostly affected indirectly through its trade relations. By contrast to the United States, recent intensification of the trade relations with China leaves the European Union better prepared for the import of production losses in the future.
Earth’s surface temperature will continue to rise for another 20 to 30 years even with the strongest carbon emission reduction currently considered. The associated changes in rainfall patterns can result in an increased flood risk worldwide. We compute the required increase in flood protection to keep high-end fluvial flood risk at present levels. The analysis is carried out worldwide for subnational administrative units. Most of the United States, Central Europe, and Northeast and West Africa, as well as large parts of India and Indonesia, require the strongest adaptation effort. More than half of the United States needs to at least double their protection within the next two decades. Thus, the need for adaptation to increased river flood is a global problem affecting industrialized regions as much as developing countries.
Climate change affects societies across the globe in various ways. In addition to gradual changes in temperature and other climatic variables, global warming is likely to increase intensity and frequency of extreme weather events.
Beyond biophysical impacts, these also directly affect societal and economic activity. Additionally, indirect effects can occur; spatially, economic losses can spread along global supply-chains; temporally, climate impacts can change the economic development trajectory of countries.
This thesis first examines how climate change alters river flood risk and its local socio-economic implications. Then, it studies the global economic response to river floods in particular, and to climate change in general.
Changes in high-end river flood risk are calculated for the next three decades on a global scale with high spatial resolution. In order to account for uncertainties, this assessment makes use of an ensemble of climate and hydrological models as well as a river routing model, that is found to perform well regarding peak river discharge. The results show an increase in high-end flood risk in many parts of the world, which require profound adaptation efforts. This pressure to adapt is measured as the enhancement in protection level necessary to stay at historical high-end risk. In developing countries as well as in industrialized regions, a high pressure to adapt is observed - the former to increase low protection levels, the latter to maintain the low risk levels perceived in the past.
Further in this thesis, the global agent-based dynamic supply-chain model acclimate is developed. It models the cascading of indirect losses in the global supply network. As an anomaly model its agents - firms and consumers - maximize their profit locally to respond optimally to local perturbations. Incorporating quantities as well as prices on a daily basis, it is suitable to dynamically resolve the impacts of unanticipated climate extremes.
The model is further complemented by a static measure, which captures the inter-dependencies between sectors across regions that are only connected indirectly. These higher-order dependencies are shown to be important for a comprehensive assessment of loss-propagation and overall costs of local disasters.
In order to study the economic response to river floods, the acclimate model is driven by flood simulations. Within the next two decades, the increase in direct losses can only partially be compensated by market adjustments, and total losses are projected to increase by 17% without further adaptation efforts. The US and the EU are both shown to receive indirect losses from China, which is strongly affected directly. However, recent trends in the trade relations leave the EU in a better position to compensate for these losses.
Finally, this thesis takes a broader perspective when determining the investment response to the climate change damages employing the integrated assessment model DICE. On an optimal economic development path, the increase in damages is anticipated as emissions and consequently temperatures increase. This leads to a significant devaluation of investment returns and the income losses from climate damages almost double.
Overall, the results highlight the need to adapt to extreme weather events - local physical adaptation measures have to be combined with regional and global policy measures to prepare the global supply-chain network to climate change.
The Red Indian Line (RIL) in central Newfoundland is the suture, where the main tract of the Iapetus Ocean was closed at similar to 452 Ma during accretion of the peri-Gondwanan Victoria arc with the composite active Laurentian margin. The protracted deformation history of this soft collision started at similar to 471 Ma with accretion of oceanic terranes to the active composite Laurentian margin. After Iapetus closure both colliding active margins were progressively deformed and metamorphosed during Silurian and Devonian (Salinic, Acadian and Neoacadian orogenic cycles). Peak conditions of the very low- to medium-grade, heterogeneously distributed metamorphism were determined by pseudosection techniques within the range of 2-7 kbar, 230-450 degrees C during increase of the metamorphic field gradient from similar to 12 degrees C/km to similar to 32 degrees C/km over time. Multiple metamorphic crystallisation stages were dated by white mica Ar-40/Ar-39 spot and plateau ages, additional Rb-Sr mineral isochrons involving white mica and one U/Pb age of titanite. All resulting ages between 439 +/- 4 Ma and 356 +/- 16 Ma postdate the closure of Iapetus. Results differ along two transects: The oldest ages of 443-421 Ma (Salinic orogenic cycle) were observed along the northern transect through the RIL zone with minimal younger overprint. Hence low temperature, intermediate to high pressure conditions (4.0-7.0 kbar, 230-340 degrees C) achieved during Taconic-Salinic underthrusting are well preserved. During Acadian dextral transpression the Taconic-Salinic structural wedge was tilted subvertically. In contrast, rocks along the southern transect through the RIL zone mainly show Acadian ages of 408-390 Ma with local preservation of older ages. Acadian deformation occurred under low temperature/low pressure conditions (similar to 250-450 degrees C, 2.5-4.6 kbar). Also Silurian terrestrial cover rocks were buried under these conditions. Acadian-Neoacadian deformation (393-340 Ma) becomes younger towards the northwest and progressively localized in transcurrent fault zones. This final foreland deformation at shallow crustal level established the Acadian/Neoacadian orogenic front in central Newfoundland slightly northwest of the RIL.