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The authors report on the fabrication of a thermoresponsive biosensor for the amperometric detection of glucose. Screen printed electrodes with heatable gold working electrodes were modified by a thermoresponsive statistical copolymer [polymer I: poly(omega-ethoxytriethylenglycol methacrylate-omega-3-(N,N-dimethyl-N-2-methacryloyloxyethyl ammonio) propanesulfonate-co-omega-butoxydiethylenglycol methacrylate-co-2-(4-benzoyl-phenoxy)ethyl methacrylate)] with a lower critical solution temperature of around 28 degrees C in aqueous solution via electrochemically induced codeposition with a pH-responsive redox-polymer [polymer II: poly(glycidyl methacrylate-co-allyl methacrylate-co-poly(ethylene glycol) methacrylate-co-butyl acrylate-co-2-(dimethylamino) ethyl methacrylate)-[Os(bpy)(2)(4-(((2-(2-(2-aminoethoxy) ethoxy) ethyl) amino) methyl)-N,N-dimethylpicolinamide)](2+)] and pyrroloquinoline quinone-soluble glucose dehydrogenase acting as biological recognition element. Polymer II bears covalently bound Os-complexes that act as redox mediators for shuttling electrons between the enzyme and the electrode surface. Polymer I acts as a temperature triggered immobilization matrix. Probing the catalytic current as a function of the working electrode temperature shows that the activity of the biosensor is dramatically reduced above the phase transition temperature of polymer I. Thus, the local modulation of the temperature at the interphase between the electrode and the bioactive layer allows switching the biosensor from an on-to an off-state without heating of the surrounding analyte solution. (C) 2015 American Vacuum Society.
Phenothiazine-modified redox hydrogels were synthesized and used for the wiring of the aldehyde oxidoreductase PaoABC to electrode surfaces. The effects of the pH value and electrode surface modification on the biocatalytic activity of the layers were studied in the presence of vanillin as the substrate. The enzyme electrodes were successfully employed as bioanodes in vanillin/O-2 biofuel cells in combination with a high potential bilirubin oxidase biocathode. Open circuit voltages of around 700 mV could be obtained in a two compartment biofuel cell setup. Moreover, the use of a rather hydrophobic polymer with a high degree of crosslinking sites ensures the formation of stable polymer/enzyme films which were successfully used as bioanode in membrane-less biofuel cells. (C) 2015 Elsevier B.V. All rights reserved.
p-Type Doping of Poly(3-hexylthiophene) with the Strong Lewis Acid Tris(pentafluorophenyl)borane
(2016)
State-of-the-art p-type doping of organic semiconductors is usually achieved by employing strong -electron acceptors, a prominent example being tetrafluorotetracyanoquinodimethane (F(4)TCNQ). Here, doping of the semiconducting model polymer poly(3-hexylthiophene), P3HT, using the strong Lewis acid tris(pentafluorophenyl)borane (BCF) as a dopant, is investigated by admittance, conductivity, and electron paramagnetic resonance measurements. The electrical characteristics of BCF- and F(4)TCNQ-doped P3HT layers are shown to be very similar in terms of the mobile hole density and the doping efficiency. Roughly 18% of the employed dopants create mobile holes in either F-4 TCNQ- or BCF-doped P3HT, while the majority of doping-induced holes remain strongly Coulomb-bound to the dopant anions. Despite similar hole densities, conductivity and hole mobility are higher in BCF-doped P3HT layers than in F(4)TCNQ-doped samples. This and the good solubility in many organic solvents render BCF very useful for p-type doping of organic semiconductors.
Stable-isotopic and sedimentary records from the orogenic Puna Plateau of NW Argentina and adjacent intermontane basins to the east furnish a unique late Cenozoic record of range uplift and ensuing paleoenvironmental change in the south-central Andes. Today, focused precipitation in this region occurs along the eastern, windward flanks of the Eastern Cordillera and Sierras Pampeanas ranges, while the orogen interior constitutes high-elevation regions with increasingly arid conditions in a westward direction. As in many mountain belts, such hydrologic and topographic gradients are commonly mirrored by a systematic relationship between the oxygen and hydrogen stable isotope ratios of meteoric water and elevation. The glass fraction of isotopically datable volcanic ash intercalated in sedimentary sequences constitutes an environmental proxy that retains a signal of the hydrogen-isotopic composition of ancient precipitation. This isotopic composition thus helps to elucidate the combined climatic and tectonic processes associated with topographic growth, which ultimately controls the spatial patterns of precipitation in mountain belts. However, between 25.5 and 27 degrees S present-day river-based hydrogen isotope lapse rates are very low, possibly due to deep-convective seasonal storms that dominate runoff. If not accounted for, the effects of such conditions on moisture availability in the past may lead to misinterpretations of proxy-records of rainfall. Here, we present hydrogen-isotope data of volcanic glass (delta Dg), extracted from 34 volcanic ash layers in different sedimentary basins of the Eastern Cordillera and the Sierras Pampeanas. Combined with previously published delta Dg records and our refined U-Pb and (U-Th)/He zircon geochronology on 17 tuff samples, we demonstrate hydrogen-isotope variations associated with paleoenvironmental change in the Angastaco Basin, which evolved from a contiguous foreland to a fault-bounded intermontane basin during the late Mio-Pliocene. We unravel the environmental impact of Mio-Pliocene topographic growth and associated orographic effects on long-term hydrogen-isotope records of rainfall in the south-central Andes, and potentially identify temporal variations in regional isotopic lapse rates that may also apply to other regions with similar topographic boundary conditions. (C) 2016 Elsevier B.V. All rights reserved.
Interplay of coupling and common noise at the transition to synchrony in oscillator populations
(2016)
There are two ways to synchronize oscillators: by coupling and by common forcing, which can be pure noise. By virtue of the Ott-Antonsen ansatz for sine-coupled phase oscillators, we obtain analytically tractable equations for the case where both coupling and common noise are present. While noise always tends to synchronize the phase oscillators, the repulsive coupling can act against synchrony, and we focus on this nontrivial situation. For identical oscillators, the fully synchronous state remains stable for small repulsive coupling; moreover it is an absorbing state which always wins over the asynchronous regime. For oscillators with a distribution of natural frequencies, we report on a counter-intuitive effect of dispersion (instead of usual convergence) of the oscillators frequencies at synchrony; the latter effect disappears if noise vanishes.
Interplay of coupling and common noise at the transition to synchrony in oscillator populations
(2016)
There are two ways to synchronize oscillators: by coupling and by common forcing, which can be pure noise. By virtue of the Ott-Antonsen ansatz for sine-coupled phase oscillators, we obtain analytically tractable equations for the case where both coupling and common noise are present. While noise always tends to synchronize the phase oscillators, the repulsive coupling can act against synchrony, and we focus on this nontrivial situation. For identical oscillators, the fully synchronous state remains stable for small repulsive coupling; moreover it is an absorbing state which always wins over the asynchronous regime. For oscillators with a distribution of natural frequencies, we report on a counter-intuitive effect of dispersion (instead of usual convergence) of the oscillators frequencies at synchrony; the latter effect disappears if noise vanishes.
Food and fear
(2016)
Lyapunov Exponents
(2016)
Lyapunov exponents lie at the heart of chaos theory, and are widely used in studies of complex dynamics. Utilising a pragmatic, physical approach, this self-contained book provides a comprehensive description of the concept. Beginning with the basic properties and numerical methods, it then guides readers through to the most recent advances in applications to complex systems. Practical algorithms are thoroughly reviewed and their performance is discussed, while a broad set of examples illustrate the wide range of potential applications. The description of various numerical and analytical techniques for the computation of Lyapunov exponents offers an extensive array of tools for the characterization of phenomena such as synchronization, weak and global chaos in low and high-dimensional set-ups, and localization. This text equips readers with all the investigative expertise needed to fully explore the dynamical properties of complex systems, making it ideal for both graduate students and experienced researchers.
Randomly coupled neural fields demonstrate irregular variation of firing rates, if the coupling is strong enough, as has been shown by Sompolinsky et al. [Phys. Rev. Lett. 61, 259 (1988)]. We present a method for reconstruction of the coupling matrix from a time series of irregular firing rates. The approach is based on the particular property of the nonlinearity in the coupling, as the latter is determined by a sigmoidal gain function. We demonstrate that for a large enough data set and a small measurement noise, the method gives an accurate estimation of the coupling matrix and of other parameters of the system, including the gain function.
Effective classroom management is considered a key criterion to making classrooms effective learning environments. Supporting classroom orchestration—the teacher-centric real-time management of classroom activities—is central to achieving effective classroom management. However, the multi-faceted nature of classroom orchestration, its complexity, and general classroom constraints such as time, present challenges for the effective management of the modern-day classroom environment. Though effective, most existing approaches for overcoming orchestration challenges, such as Google Classroom, are arguably ad hoc. We argue that streamlined technology-driven orchestration can be attained through the use of an orchestration workbench, potentially making educators more effective within formal learning environments. Early supporting evidence, from a study involving the use of a prototype orchestration tool, demonstrates the feasibility of organised orchestration and its potential to improve students' learning experience.
QuestionThe empirical evidence of root herbivory effects on plant community composition and co-existence is contradictory. This originates from difficulties connected to below-ground research and confinement of experimental studies to a small range of environmental conditions. Here we suggest coupling experimental data with an individual-based model to overcome the limitations inherent in either approach. To demonstrate this, we investigated the consequences of root herbivory, as experimentally observed on individual plants, on plant competition and co-existence in a population and community context under different root herbivory intensities (RHI), fluctuating and constant root herbivore activity and grazing along a resource gradient. LocationBerlin, Germany, glasshouse; Potsdam, Germany, high performance cluster computer. MethodsThe well-established community model IBC-Grass was adapted to allow for a flexible species parameterization and to include annual species. Experimentally observed root herbivory effects on performance of eight common grassland plant species were incorporated into the model by altering plant growth rates. We then determined root herbivore effects on plant populations, competitive hierarchy and consequences for co-existence and community diversity. ResultsRoot herbivory reduced individual biomass, but temporal fluctuation allowed for compensation of herbivore effects. Reducing resource availability strongly shifted competitive hierarchies, with, however, more similar hierarchies along the gradient under root herbivory, pointing to reduced ecological species differences. Consequently, negative effects on co-existence and diversity prevailed, with the exception of a few positive effects on co-existence of selected species pairs. Temporal fluctuation alleviated but did not remove negative root herbivore effects, despite of the stronger influence of intra- compared to interspecific competition. Grazing in general augmented co-existence. Most interestingly, grazing interacted with RHI and resource availability by promoting positive effects of root herbivory. ConclusionsThrough integrating experimental data on the scale of individual plants with a simulation model we verified that root herbivory could affect plant competition with consequences for species co-existence. Our approach demonstrates the benefit that accrues when empirical and modelling approaches are brought more closely together, and that gathering data on distinct processes and under specific conditions, combined with appropriate models, can be used to answer challenging research questions in a more general way.
„Vajanie iz vremeni“
(2016)
Einführung
(2016)
Blaise Pascal (1623-1662) gehört zu den größten Geistern, die je auf Erden gelebt haben. Der vorliegende Band versucht eine Verbindungslinie zwischen seiner Rechtsphilosophie und seiner Religionsphilosophie herzustellen, indem er Pascals Gedanken über die Gerechtigkeit zu seiner berühmten Lehre von den drei Ordnungen ins Verhältnis setzt.
This volume is a novel approach to the corpus-based variationist sociolinguistic study of contemporary urban western Irish English. Based on qualitative data as well as on linguistic features extracted from the Corpus of Galway City Spoken English, this study approaches the major sociolinguistic characteristics of (th) and (dh) variability in Galway City English. It demonstrates the diverse local patterns of variability and change in the phonetic realisation of the dental fricatives and establishes a considerable degree of divergence from traditional accounts on Irish English. This volume suggests that the linguistic stratification of variants of (th) and (dh) in Galway correlates both with the social stratification of the city itself and with the stratification of speakers by social status, sex/gender and age group.
Molekulare Charakterisierung von CP75, einem neuen centrosomalen Protein in Dictyostelium discoideum
(2016)
Das Centrosom ist ein Zellkern-assoziiertes Organell, das nicht von einer Membran umschlossen ist. Es spielt eine wichtige Rolle in vielen Mikrotubuli- abhängigen Prozessen wie Organellenpositionierung, Zellpolarität oder die Organisation der mitotischen Spindel. Das Centrosom von Dictyostelium besteht aus einer dreischichtigen Core-Struktur umgeben von einer Corona, die Mikrotubuli-nukleierende Komplexe enthält. Die Verdoppelung des Centrosoms in Dictyostelium findet zu Beginn der Mitose statt. In der Prophase vergrößert sich die geschichtete Core-Struktur und die Corona löst sich auf. Anschließend trennen sich die beiden äußeren Lagen der Core-Struktur und bilden in der Metaphase die beiden Spindelpole, die in der Telophase zu zwei vollständigen Centrosomen heranreifen. Das durch eine Proteom-Analyse identifizierte Protein CP75 lokalisiert am Centrosom abhängig von den Mitosephasen. Es dissoziiert von der Core-Struktur in der Prometaphase und erscheint an den Spindelpolen in der Telophase wieder. Dieses Verhalten korreliert mit dem Verhalten der mittleren Lage der Core-Struktur in der Mitose, was darauf hinweist, dass CP75 eine Komponente dieser Schicht sein könnte. Die FRAP-Experimente am Interphase- Centrosom zeigen, dass GFP-CP75 dort nicht mobil ist. Das deutet darauf hin, dass das Protein wichtige Funktionen im Strukturerhalt der centrosomalen Core- Struktur übernehmen könnte. Sowohl die C- als auch die N-terminale Domäne von CP75 enthalten centrosomale Targeting-Domäne. Als GFP-Fusionsproteine (GFP-CP75-N und -C) lokalisieren die beiden Fragmente am Centrosom in der Interphase. Während GFP-CP75-C in der Mitose am Centrosom verbleibt, verschwindet GFP-CP75-N in der Metaphase und kehrt erst in der späten Telophase zurück. GFP-CP75-C und GFP-CP75O/E kolokalisieren mit F-Aktin am Zellcortex, zeigen aber keine Interaktion mit Aktin mit der BioID-Methode. Die N-terminale Domäne von CP75 enthält eine potentielle Plk1- Phosphorylierungssequenz. Die Überexpression der nichtphosphorylierbaren Punktmutante (GFP-CP75-Plk-S143A) ruft verschiedene Phänotypen wie verlängerte oder überzählige Centrosomen, vergrößerte Zellkerne und Anreicherung von detyrosinierten Mikrotubuli hervor. Die ähnlichen Phänotypen konnten auch bei GFP-CP75-N und CP75-RNAi beobachtet werden. Der
Phänotyp der detyrosinierten Mikrotubuli bringt erstmals den Beweis dafür, dass I
in Dictyostelium posttranslationale Modifikation an Tubulinen stattfindet. Außerdem zeigten CP75-RNAi-Zellen Defekte in der Organisation der mitotischen Spindel. Mittels BioID-Methode konnten drei potentielle Interaktionspartner von CP75 identifiziert werden. Diese drei Proteine CP39, CP91 und Cep192 sind ebenfalls Bestandteile des Centrosoms.
Subcultures creating culture
(2016)
The purpose of this work is to apply the methods of textual semiotics to subcultures, in particular to the little known glam subculture. Subcultures have been the main research field of the Birmingham Centre for Contemporary Cultural Studies, known for its interdisciplinary approach, and for its focus on the creative aspects of subculture. Hebdige, in particular, introduced many semiotic elements in his work, as the aberrant decoding after Eco and the cultural creativity via bricolage after Lévi-Strauss. His definition of subculture as symbolic resistance has been criticized by the following post-subcultural researchers for its abstractness and lack of cohesion.
Semiotics eventually have been expelled from the set of tools used in sociology for the analysis of subcultures. Nowadays, the studies on subcultures have a strong ethnographic focus. Due to terminological proliferation and a descriptive approach, it is difficult to compare them on a common basis.
Textual semiotics, through the concept of semiosphere developed by Lotman, allows to go back to the intuitions of Hebdige, organizing the semiotic elements already present in his work into a wider system of interpretation. The semiosphere offers a coherent theoretical horizon as a basis for further analysis, and a new methodological perspective focusing on the cultural. In this thesis for the first time the work of Lotman is applied to the study of a subculture.
For the first time a molecularly imprinted polymer (MIP) with direct electron transfer (DET) and bioelectrocatalytic activity of the target protein is presented. Thin films of MIPs for the recognition of a hexameric tyrosine-coordinated heme protein (HTHP) have been prepared by electropolymerization of scopoletin after oriented assembly of HTHP on a self-assembled monolayer (SAM) of mercaptoundecanoic acid (MUA) on gold electrodes. Cavities which should resemble the shape and size of HTHP were formed by template removal. Rebinding of the target protein sums up the recognition by non-covalent interactions between the protein and the MIP with the electrostatic attraction of the protein by the SAM. HTHP bound to the MIP exhibits quasi-reversible DET which is reflected by a pair of well pronounced redox peaks in the cyclic voltammograms (CVs) with a formal potential of -184.4 +/- 13.7 mV vs. Ag/AgCl (1 M KCl) at pH 8.0 and it was able to catalyze the cathodic reduction of peroxide. At saturation the MIP films show a 12-fold higher electroactive surface concentration of HTHP than the non-imprinted polymer (NIP).
Tarkovsky’s legacy
(2016)
Multimodel comparison of the ionosphere variability during the 2009 sudden stratosphere warming
(2016)
A comparison of different model simulations of the ionosphere variability during the 2009 sudden stratosphere warming (SSW) is presented. The focus is on the equatorial and low-latitude ionosphere simulated by the Ground-to-topside model of the Atmosphere and Ionosphere for Aeronomy (GAIA), Whole Atmosphere Model plus Global Ionosphere Plasmasphere (WAM+GIP), and Whole Atmosphere Community Climate Model eXtended version plus Thermosphere-Ionosphere-Mesosphere-Electrodynamics General Circulation Model (WACCMX+TIMEGCM). The simulations are compared with observations of the equatorial vertical plasma drift in the American and Indian longitude sectors, zonal mean Fregion peak density (NmF2) from the Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC) satellites, and ground-based Global Positioning System (GPS) total electron content (TEC) at 75 degrees W. The model simulations all reproduce the observed morning enhancement and afternoon decrease in the vertical plasma drift, as well as the progression of the anomalies toward later local times over the course of several days. However, notable discrepancies among the simulations are seen in terms of the magnitude of the drift perturbations, and rate of the local time shift. Comparison of the electron densities further reveals that although many of the broad features of the ionosphere variability are captured by the simulations, there are significant differences among the different model simulations, as well as between the simulations and observations. Additional simulations are performed where the neutral atmospheres from four different whole atmosphere models (GAIA, HAMMONIA (Hamburg Model of the Neutral and Ionized Atmosphere), WAM, and WACCMX) provide the lower atmospheric forcing in the TIME-GCM. These simulations demonstrate that different neutral atmospheres, in particular, differences in the solar migrating semidiurnal tide, are partly responsible for the differences in the simulated ionosphere variability in GAIA, WAM+GIP, and WACCMX+TIMEGCM.
The production of toxic metabolites by cyanobacterial blooms represents a significant threat to the health of humans and ecosystems worldwide. Here we summarize the current state of the knowledge regarding the genetics, biosynthesis and regulation of well-characterized cyanotoxins, including the microcystins, nodularin, cylindrospermopsin, saxitoxins and antitoxins, as well as the lesser-known marine toxins (e.g. lyngbyatoxin, aplysiatoxin, jamaicamides, barbamide, curacin, hectochlorin and apratoxins). (C) 2015 Elsevier B.V. All rights reserved.
Background
Dietary calcium (Ca) concentrations might affect regulatory pathways within the Ca and vitamin D metabolism and consequently excretory mechanisms. Considering large variations in Ca concentrations of feline diets, the physiological impact on Ca homeostasis has not been evaluated to date. In the present study, diets with increasing concentrations of dicalcium phosphate were offered to ten healthy adult cats (Ca/phosphorus (P): 6.23/6.02, 7.77/7.56, 15.0/12.7, 19.0/17.3, 22.2/19.9, 24.3/21.6 g/kg dry matter). Each feeding period was divided into a 10-day adaptation and an 8-day sampling period in order to collect urine and faeces. On the last day of each feeding period, blood samples were taken.
Results
Urinary Ca concentrations remained unaffected, but faecal Ca concentrations increased (P < 0.001) with increasing dietary Ca levels. No effect on whole and intact parathyroid hormone levels, fibroblast growth factor 23 and calcitriol concentrations in the blood of the cats were observed. However, the calcitriol precursors 25(OH)D-2 and 25(OH)D-3, which are considered the most useful indicators for the vitamin D status, decreased with higher dietary Ca levels (P = 0.013 and P = 0.033). Increasing dietary levels of dicalcium phosphate revealed an acidifying effect on urinary fasting pH (6.02) and postprandial pH (6.01) (P < 0.001), possibly mediated by an increase of urinary phosphorus (P) concentrations (P < 0.001).
Conclusions
In conclusion, calcitriol precursors were linearly affected by increasing dietary Ca concentrations. The increase in faecal Ca excretion indicates that Ca homeostasis of cats is mainly regulated in the intestine and not by the kidneys. Long-term studies should investigate the physiological relevance of the acidifying effect observed when feeding diets high in Ca and P.
Mujeres de apocalipsis
(2016)
Mujeres del Apocalipsis propone nuevas lecturas de género en relación a las mujeres piadosas que habitaron Nueva España en el siglo XVIII. El estudio sebasa en un corpus de los archivos de sus procesos inquisitoriales, mucho de ellos aún indéditos. Estas mujeres ganaron libertad y accedieon a una parcial autonomía en el mundo colonial. A través de su lectura, se descubren las estrategías tácticas a través de las cuales las beatas pactaron una nueva forma de se mujer en aquella era.
The fruit of Aristotelia chilensis is considered a "super fruit" due to its high concentration of polyphenols displaying exceptional antioxidant capacities ORAC. From maqui berries have been reported several anthocyanins and glycosylated flavonoids, those benefits increase the attention to restudy the plant. From the leaves of A. chilensis several indole alkaloids have been reported, we in addition to aristoteline, aristone, aristoquinoline and 3-fromylindole report the spectroscopic elucidation of 8-oxo-9-dehydromakomakine (1), hobartine (2) and a new alkaloid named 8-oxohobartine (3). Compound 1 to 3 did not show bactericidal activity against E. coli and S. aureus till 200 mu g.
"Meine Vorbilder und Quellen sind meistens wesentlich älter als die, die mir vorgeworfen werden. Ich stehle nur von den besten." Dieser Kommentar, mit dem sich der Autor und Zeichner Walter Moers 2004 in einem Interview mit der Frankfurter Allgemeinen Zeitung zu der visuellen Ausrichtung seines Werks äußert, lässt sich ohne Weiteres auch auf die sechs Bände seiner Zamonien-Reihe übertragen. Diese sogenannten Zamonien-Romane, ,Die 13 Leben des Käpt'n Blaubär' (1999), ,Ensel und Krete' (2000), ,Rumo & Die Wunder im Dunkeln' (2003), ,Die Stadt der Träumenden Bücher' (2004), ,Der Schrecksenmeister' (2007) und ,Das Labyrinth der Träumenden Bücher' (2011), werden in den wenigen bisher erschienen Forschungsaufsätzen mit Vorliebe als Fantasy-Literatur klassifiziert, die sich originellerweise allen Gesetzen des Genres widersetze.
Die vorliegende Arbeit zeigt dagegen auf, dass sich Walter Moers mit seinen Werken zuallererst an einer lange von der Forschung vernachlässigten Tradition satirischen Schreibens orientiert. Dabei spannt die Untersuchung einen Bogen, der von den lehrreichen platonischen Mythen bis zu den erkenntnisfördernden Zamonien-Erzählungen reicht, der in der Antike bei dem Begründer der Prosasatire Menippos von Gadara ansetzt und sich bis zum Gegenwartsautoren Walter Moers erstreckt.
Polychlorinated biphenyls (PCBs) can cause endocrine disruption, cancer, immunosuppression, or reproductive failure in animals. We used an individual-based model to explore whether and how PCB-associated reproductive failure could affect the dynamics of a hypothetical polar bear (Ursus maritimus) population exposed to PCBs to the same degree as the East Greenland subpopulation. Dose-response data from experimental studies on a surrogate species, the mink (Mustela vision), were used in the absence of similar data for polar bears. Two alternative types of reproductive failure in relation to maternal sum-PCB concentrations were considered: increased abortion rate and increased cub mortality. We found that the quantitative impact of PCB-induced reproductive failure on population growth rate depended largely on the actual type of reproductive failure involved. Critical potencies of the dose-response relationship for decreasing the population growth rate were established for both modeled types of reproductive failure. Comparing the model predictions of the age-dependent trend of sum-PCBs concentrations in females with actual field measurements from East Greenland indicated that it was unlikely that PCB exposure caused a high incidence of abortions in the subpopulation. However, on the basis of this analysis, it could not be excluded that PCB exposure contributes to higher cub mortality. Our results highlight the necessity for further research on the possible influence of PCBs on polar bear reproduction regarding their physiological pathway. This includes determining the exact cause of reproductive failure, i.e., in utero exposure versus lactational exposure of offspring; the timing of offspring death; and establishing the most relevant reference metrics for the dose-response relationship.
We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε ∼ 5 × 10−4 is calibrated by ultrafast X-ray diffraction.
We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain epsilon similar to 5 x 10(-4) is calibrated by ultrafast X-ray diffraction.
On the basis of the layer-by-layer deposition of polyelectrolytes, we have designed hybrid nanolayer composites for integrated optoacoustic experiments. The femtosecond-laser-excitation of an Azo functionalized film launches nanoscale strain waves at GHz frequencies into a transparent polymer layer. Gold nanorods deposited on the surface sense the arrival of these hyper-sound-waves on the picosecond time scale via a modification of their longitudinal plasmon resonance. We simulated the strain waves using a simple linear masses-and-springs model, which yields good agreement with the observed time scales associated with the nanolayer thicknesses of the constituent materials. From systematic experiments with calibrated strain amplitudes we conclude that reversible viscoelastic deformations of the polyelectrolyte multilayers are triggered by ultrashort pressure transients of about 4 MPa. Our experiments show that strain-mediated interactions in nanoarchitectures composed of molecular photoswitches and plasmonic particles may be used to design new functionalities. The approach combines the highly flexible and cost-effective preparation of polyelectrolyte multilayers with ultrafast molecular strain actuation and plasmonic sensing. Although we use simple flat layered structures for demonstration, this new concept can be used for three-dimensional nanoassemblies with different functionalities. The ultrafast and reversible nature of the response is highly desirable, and the short wavelength associated with the high frequency of the hyper-sound-waves connecting photoactive molecules and nanoparticles inherently gives spectroscopic access to the nanoscale. High-frequency elastic moduli are derived from the ultrafast spectroscopy of the hypersonic response in polyelectrolyte multilayers.
The goal of the presented work is to explore the interaction between gold nanorods (GNRs) and hyper-sound waves. For the generation of the hyper-sound I have used Azobenzene-containing polymer transducers. Multilayer polymer structures with well-defined thicknesses and smooth interfaces were built via layer-by-layer deposition. Anionic polyelectrolytes with Azobenzene side groups (PAzo) were alternated with cationic polymer PAH, for the creation of transducer films. PSS/PAH multilayer were built for spacer layers, which do not absorb in the visible light range. The properties of the PAzo/PAH film as a transducer are carefully characterized by static and transient optical spectroscopy. The optical and mechanical properties of the transducer are studied on the picosecond time scale. In particular the relative change of the refractive index of the photo-excited and expanded PAH/PAzo is Δn/n = - 2.6*10‐4. Calibration of the generated strain is performed by ultrafast X-ray diffraction calibrated the strain in a Mica substrate, into which the hyper-sound is transduced. By simulating the X-ray data with a linear-chain-model the strain in the transducer under the excitation is derived to be Δd/d ~ 5*10‐4.
Additional to the investigation of the properties of the transducer itself, I have performed a series of experiments to study the penetration of the generated strain into various adjacent materials. By depositing the PAzo/PAH film onto a PAH/PSS structure with gold nanorods incorporated in it, I have shown that nanoscale impurities can be detected via the scattering of hyper-sound.
Prior to the investigation of complex structures containing GNRs and the transducer, I have performed several sets of experiments on GNRs deposited on a small buffer of PSS/PAH. The static and transient response of GNRs is investigated for different fluence of the pump beam and for different dielectric environments (GNRs covered by PSS/PAH).
A systematic analysis of sample architectures is performed in order to construct a sample with the desired effect of GNRs responding to the hyper-sound strain wave. The observed shift of a feature related to the longitudinal plasmon resonance in the transient reflection spectra is interpreted as the event of GNRs sensing the strain wave. We argue that the shift of the longitudinal plasmon resonance is caused by the viscoelastic deformation of the polymer around the nanoparticle. The deformation is induced by the out of plane difference in strain in the area directly under a particle and next to it. Simulations based on the linear chain model support this assumption. Experimentally this assumption is proven by investigating the same structure, with GNRs embedded in a PSS/PAH polymer layer.
The response of GNRs to the hyper-sound wave is also observed for the sample structure with GNRs embedded in PAzo/PAH films. The response of GNRs in this case is explained to be driven by the change of the refractive index of PAzo during the strain propagation.
A convenient and general synthesis of 2-thiocarbohydrates via cerium ammonium nitrate oxidation of the thiocyanate ion is described. Radical addition to glycals proceeds with excellent regio- and good stereoselectivities in only one step, deprotection affords water-soluble 2-thio saccharides. Binding studies to Con A have been performed by isothermal titration calorimetry (ITC) and saturation transfer difference (STD) NMR spectroscopy. The 2-thiomannose derivative binds even stronger to Con A than the natural substrate, offering opportunities for new lectin or enzyme inhibitors.
Time-delayed collection field experiments are applied to planar organometal halide perovskite (CH3NH3PbI3) based solar cells to investigate charge carrier recombination in a fully working solar cell at the nanosecond to microsecond time scale. Recombination of mobile (extractable) charges is shown to follow second-order recombination dynamics for all fluences and time scales tested. Most importantly, the bimolecular recombination coefficient is found to be time-dependent, with an initial value of ca. 10(-9) cm(3)/s and a progressive reduction within the first tens of nanoseconds. Comparison to the prototypical organic bulk heterojunction device PTB7:PC71BM yields important differences with regard to the mechanism and time scale of free carrier recombination. (C) 2016 AIP Publishing LLC.
Voltage-gated sodium channels, Nav1, play a crucial role in the generation and propagation of action potentials and substantially contribute to the shape of their rising phase. The electric organ discharge (EOD) of African weakly electric fish (Mormyroidea) is the sum of action potentials fired from all electrocytes of the electric organ at the same time and hence voltage-gated sodium channels are one factor—together with the electrocyte’s morphology and innervation pattern—that determines the properties of these EODs. Due to the fish-specific genome duplication, teleost fish possess eight copies of sodium channel genes (SCN), which encode for Nav1 channels. In mormyroids, SCN4aa is solely expressed in the electrocytes of the adult electric organ. In this study, we compared entire SCN4aa sequences of six species of the genus Campylomormyrus and identified nonsynonymous substitutions among them. SCN4aa in Campylomormyrus exhibits a much higher evolutionary rate compared to its paralog SCN4ab, whose expression is not restricted to the electric organ. We also found evidence for strong positive selection on the SCN4aa gene within Mormyridae and along the lineage ancestral to the Mormyridae. We have identified sites at which all nonelectric teleosts are monomorphic in their amino acid, but mormyrids have different amino acids. Our findings confirm the crucial role of SCN4aa in EOD evolution among mormyrid weakly electric fish. The inferred positive selection within Mormyridae makes this gene a prime candidate for further investigation of the divergent evolution of pulse-type EODs among closely related species.
It has been proposed that in online sentence comprehension the dependency between a reflexive pronoun such as himself/herself and its antecedent is resolved using exclusively syntactic constraints. Under this strictly syntactic search account, Principle A of the binding theory which requires that the antecedent c-command the reflexive within the same clause that the reflexive occurs in constrains the parser's search for an antecedent. The parser thus ignores candidate antecedents that might match agreement features of the reflexive (e.g., gender) but are ineligible as potential antecedents because they are in structurally illicit positions. An alternative possibility accords no special status to structural constraints: in addition to using Principle A, the parser also uses non-structural cues such as gender to access the antecedent. According to cue -based retrieval theories of memory (e.g., Lewis and Vasishth, 2005), the use of non-structural cues should result in increased retrieval times and occasional errors when candidates partially match the cues, even if the candidates are in structurally illicit positions. In this paper, we first show how the retrieval processes that underlie the reflexive binding are naturally realized in the Lewis and Vasishth (2005) model. We present the predictions of the model under the assumption that both structural and non-structural cues are used during retrieval, and provide a critical analysis of previous empirical studies that failed to find evidence for the use of non-structural cues, suggesting that these failures may be Type II errors. We use this analysis and the results of further modeling to motivate a new empirical design that we use in an eye tracking study. The results of this study confirm the key predictions of the model concerning the use of non-structural cues, and are inconsistent with the strictly syntactic search account. These results present a challenge for theories advocating the infallibility of the human parser in the case of reflexive resolution, and provide support for the inclusion of agreement features such as gender in the set of retrieval cues.
It has been proposed that in online sentence comprehension the dependency between a reflexive pronoun such as himself/herself and its antecedent is resolved using exclusively syntactic constraints. Under this strictly syntactic search account, Principle A of the binding theory—which requires that the antecedent c-command the reflexive within the same clause that the reflexive occurs in—constrains the parser's search for an antecedent. The parser thus ignores candidate antecedents that might match agreement features of the reflexive (e.g., gender) but are ineligible as potential antecedents because they are in structurally illicit positions. An alternative possibility accords no special status to structural constraints: in addition to using Principle A, the parser also uses non-structural cues such as gender to access the antecedent. According to cue-based retrieval theories of memory (e.g., Lewis and Vasishth, 2005), the use of non-structural cues should result in increased retrieval times and occasional errors when candidates partially match the cues, even if the candidates are in structurally illicit positions. In this paper, we first show how the retrieval processes that underlie the reflexive binding are naturally realized in the Lewis and Vasishth (2005) model. We present the predictions of the model under the assumption that both structural and non-structural cues are used during retrieval, and provide a critical analysis of previous empirical studies that failed to find evidence for the use of non-structural cues, suggesting that these failures may be Type II errors. We use this analysis and the results of further modeling to motivate a new empirical design that we use in an eye tracking study. The results of this study confirm the key predictions of the model concerning the use of non-structural cues, and are inconsistent with the strictly syntactic search account. These results present a challenge for theories advocating the infallibility of the human parser in the case of reflexive resolution, and provide support for the inclusion of agreement features such as gender in the set of retrieval cues.
Individuals with agrammatic Broca's aphasia experience difficulty when processing reversible non-canonical sentences. Different accounts have been proposed to explain this phenomenon. The Trace Deletion account (Grodzinsky, 1995, 2000, 2006) attributes this deficit to an impairment in syntactic representations, whereas others (e.g., Caplan, Waters, Dede, Michaud, & Reddy, 2007; Haarmann, Just, & Carpenter, 1997) propose that the underlying structural representations are unimpaired, but sentence comprehension is affected by processing deficits, such as slow lexical activation, reduction in memory resources, slowed processing and/or intermittent deficiency, among others. We test the claims of two processing accounts, slowed processing and intermittent deficiency, and two versions of the Trace Deletion Hypothesis (TDH), in a computational framework for sentence processing (Lewis & Vasishth, 2005) implemented in ACT-R (Anderson, Byrne, Douglass, Lebiere, & Qin, 2004). The assumption of slowed processing is operationalized as slow procedural memory, so that each processing action is performed slower than normal, and intermittent deficiency as extra noise in the procedural memory, so that the parsing steps are more noisy than normal. We operationalize the TDH as an absence of trace information in the parse tree. To test the predictions of the models implementing these theories, we use the data from a German sentence—picture matching study reported in Hanne, Sekerina, Vasishth, Burchert, and De Bleser (2011). The data consist of offline (sentence-picture matching accuracies and response times) and online (eye fixation proportions) measures. From among the models considered, the model assuming that both slowed processing and intermittent deficiency are present emerges as the best model of sentence processing difficulty in aphasia. The modeling of individual differences suggests that, if we assume that patients have both slowed processing and intermittent deficiency, they have them in differing degrees.
Background. The bay cat Catopuma badia is endemic to Borneo, whereas its sister species the Asian golden cat Catopuma temminckii is distributed from the Himalayas and southern China through Indochina, Peninsular Malaysia and Sumatra. Based onmorphological data, up to five subspecies of the Asian golden cat have been recognized, but a taxonomic assessment, including molecular data and morphological characters, is still lacking. Results. We combined molecular data (whole mitochondrial genomes), morphological data (pelage) and species distribution projections (up to the Late Pleistocene) to infer how environmental changes may have influenced the distribution of these sister species over the past 120 000 years. The molecular analysis was based on sequenced mitogenomes of 3 bay cats and 40 Asian golden cats derived mainly from archival samples. Our molecular data suggested a time of split between the two species approximately 3.16 Ma and revealed very low nucleotide diversity within the Asian golden cat population, which supports recent expansion of the population. Discussion. The low nucleotide diversity suggested a population bottleneck in the Asian golden cat, possibly caused by the eruption of the Toba volcano in Northern Sumatra (approx. 74 kya), followed by a continuous population expansion in the Late Pleistocene/Early Holocene. Species distribution projections, the reconstruction of the demographic history, a genetic isolation-by-distance pattern and a gradual variation of pelage pattern support the hypothesis of a post-Toba population expansion of the Asian golden cat from south China/Indochina to PeninsularMalaysia and Sumatra. Our findings reject the current classification of five subspecies for the Asian golden cat, but instead support either a monotypic species or one comprising two subspecies: (i) the Sunda golden cat, distributed south of the Isthmus of Kra: C. t. temminckii and (ii) Indochinese, Indian, Himalayan and Chinese golden cats, occurring north of the Isthmus: C. t. moormensis.
Background Dietary calcium (Ca) concentrations might affect regulatory pathways within the Ca and vitamin D metabolism and consequently excretory mechanisms. Considering large variations in Ca concentrations of feline diets, the physiological impact on Ca homeostasis has not been evaluated to date. In the present study, diets with increasing concentrations of dicalcium phosphate were offered to ten healthy adult cats (Ca/phosphorus (P): 6.23/6.02, 7.77/7.56, 15.0/12.7, 19.0/17.3, 22.2/19.9, 24.3/21.6 g/kg dry matter). Each feeding period was divided into a 10-day adaptation and an 8-day sampling period in order to collect urine and faeces. On the last day of each feeding period, blood samples were taken. Results Urinary Ca concentrations remained unaffected, but faecal Ca concentrations increased (P < 0.001) with increasing dietary Ca levels. No effect on whole and intact parathyroid hormone levels, fibroblast growth factor 23 and calcitriol concentrations in the blood of the cats were observed. However, the calcitriol precursors 25(OH)D-2 and 25(OH)D-3, which are considered the most useful indicators for the vitamin D status, decreased with higher dietary Ca levels (P = 0.013 and P = 0.033). Increasing dietary levels of dicalcium phosphate revealed an acidifying effect on urinary fasting pH (6.02) and postprandial pH (6.01) (P < 0.001), possibly mediated by an increase of urinary phosphorus (P) concentrations (P < 0.001). Conclusions In conclusion, calcitriol precursors were linearly affected by increasing dietary Ca concentrations. The increase in faecal Ca excretion indicates that Ca homeostasis of cats is mainly regulated in the intestine and not by the kidneys. Long-term studies should investigate the physiological relevance of the acidifying effect observed when feeding diets high in Ca and P.
Templates of complex nanopatterns in a form of hierarchically sequenced dots and stripes can be generated in block copolymer films on lithography-free 3D topographic substrates. The approach exploits thickness- and swelling-responsive morphological behavior of block copolymers, and demonstrates novel possibilities of topography-guided registration of nanopatterns due to periodic confinement and spontaneous orthogonal flow-fields.
This is the first statistical survey of field fluctuations related with medium-scale traveling ionospheric disturbances (MSTIDs), which considers magnetic field, electric field, and plasma density variations at the same time. Midlatitude electric fluctuations (MEFs) and midlatitude magnetic fluctuations (MMFs) observed in the nighttime topside ionosphere have generally been attributed to MSTIDs. Although the topic has been studied for several decades, statistical studies of the Poynting flux related with MEF/MMF/MSTID have not yet been conducted. In this study we make use of electric/magnetic field and plasma density observations by the European Space Agency's Swarm constellation to address the statistical behavior of the Poynting flux. We have found that (1) the Poynting flux is directed mainly from the summer to winter hemisphere, (2) its magnitude is larger before midnight than thereafter, and (3) the magnitude is not well correlated with fluctuation level of in situ plasma density. These results are discussed in the context of previous studies.
We introduce a novel double-hydrophilic hydroxyethylmethacrylate (HEMA) based diblock glycopolymer which self-assembles into homogeneous spherical micellar structures in water. The micellar structure renders surface-oriented N-acetylglucocosamine (GlcNAc) sugar moieties for strong multivalent glycan-mediated lectin binding. Structural analysis and lectin binding is performed by microscopy methods, dynamic light scattering (DLS) and two-focus fluorescence correlation spectroscopy (2fFCS), revealing a novel micellar type of multivalent sugar binding scaffold with high potential for biomedical applications.
Many previous studies have shown that the turbulent mixing layer under periodic forcing tends to adopt a lock-on state, where the major portion of the fluctuations in the flow are synchronized at the forcing frequency. The goal of this experimental study is to apply closed-loop control in order to provoke the lock-on state, using information from the flow itself. We aim to determine the range of frequencies for which the closed-loop control can establish the lock-on, and what mechanisms are contributing to the selection of a feedback frequency. In order to expand the solution space for optimal closed-loop control laws, we use the genetic programming control (CPC) framework. The best closed-loop control laws obtained by CPC are analysed along with the associated physical mechanisms in the mixing layer flow. The resulting closed-loop control significantly outperforms open-loop forcing in terms of robustness to changes in the free-stream velocities. In addition, the selection of feedback frequencies is not locked to the most amplified local mode, but rather a range of frequencies around it.
Many previous studies have shown that the turbulent mixing layer under periodic forcing tends to adopt a lock-on state, where the major portion of the fluctuations in the flow are synchronized at the forcing frequency. The goal of this experimental study is to apply closed-loop control in order to provoke the lock-on state, using information from the flow itself. We aim to determine the range of frequencies for which the closed-loop control can establish the lock-on, and what mechanisms are contributing to the selection of a feedback frequency. In order to expand the solution space for optimal closed-loop control laws, we use the genetic programming control (CPC) framework. The best closed-loop control laws obtained by CPC are analysed along with the associated physical mechanisms in the mixing layer flow. The resulting closed-loop control significantly outperforms open-loop forcing in terms of robustness to changes in the free-stream velocities. In addition, the selection of feedback frequencies is not locked to the most amplified local mode, but rather a range of frequencies around it.
Hybrid terrain models combine large regular data sets and high-resolution irregular meshes [triangulated irregular network (TIN)] for topographically and morphologically complex terrain features such as man-made microstructures or cliffs. In this paper, a new method to generate and visualize this kind of 3D hybrid terrain models is presented. This method can integrate geographic data sets from multiple sources without a remeshing process to combine the heterogeneous data of the different models. At the same time, the original data sets are preserved without modification, and, thus, TIN meshes can be easily edited and replaced, among other features. Specifically, our approach is based on the utilization of the external edges of convexified TINs as the fundamental primitive to tessellate the space between both types of meshes. Our proposal is eminently parallel, requires only a minimal preprocessing phase, and minimizes the storage requirements when compared with the previous proposals.
Quantum dynamics of H-2(+) excited by two-cycle laser pulses with laser carrier frequencies corresponding to the wavelengths lambda(1) = 800 and 200 nm (corresponding to the periods tau(1) = 2.667 and 0.667 fs, respectively) and being linearly polarized along the molecular axis have been studied by the numerical solution of the non-Born-Oppenheimer time-dependent Schrodinger equation within a three-dimensional (3D) model, including the internuclear distance R and electron coordinates z and rho. The amplitudes of the pulses have been chosen such that the energies of H-2(+) after the ends of the laser pulses, < E > approximate to-0.515 au, were close to the dissociation threshold of H-2(+). It is found that there exists a certain characteristic oscillation frequency omega(osc) = 0.2278 au (corresponding to the period tau(osc) = 0.667 fs and the wavelength lambda(osc) = 200 nm) that plays the role of a "carrier" frequency of temporally shaped oscillations of the expectation values <-partial derivative V/partial derivative z) emerging after the ends of the laser pulses, both at lambda(1) = 800 nm and at lambda(1) = 200 nm. Moreover, at lambda(1) = 200 nm, the expectation value < z > also demonstrates temporally shaped oscillations after the end of the laser pulse. In contrast, at lambda(1) = 800 nm, the characteristic oscillation frequency omega(osc) = 0.2278 au appears as the frequency of small-amplitude oscillations of the slowly varying expectation value < z > which makes, after the end of the pulse, an excursion with an amplitude of about 4.5 au along the z axis and returns back to < z > approximate to 0 afterward. It is found that the period of the temporally shaped post-field oscillations of <-partial derivative V/partial derivative z > and < z >, estimated as tau(shp) approximate to 30 fs, correlates with the nuclear motion. It is also shown that vibrational excitation of H-2(+) is accompanied by the formation of "hot" and "cold" vibrational ensembles along the R degree of freedom. Power spectra related to the electron motion in H-2(+) calculated for both the laser-driven z and optically passive rho degrees of freedom in the acceleration form proved to be very interesting. In particular, both odd and even harmonics can be observed.
Storage strategies have been proposed as a run-time optimization for the PyPy Python implementation and have shown promising results for optimizing execution speed and memory requirements. However, it remained unclear whether the approach works equally well in other dynamic languages. Furthermore, while PyPy is based on RPython, a language to write VMs with reusable components such as a tracing just-in-time compiler and garbage collection, the strategies design itself was not generalized to be reusable across languages implemented using that same toolchain. In this paper, we present a general design and implementation for storage strategies and show how they can be reused across different RPython-based languages. We evaluate the performance of our implementation for RSqueak, an RPython-based VM for Squeak/Smalltalk and show that storage strategies may indeed off er performance benefits for certain workloads in other dynamic programming languages. We furthermore evaluate the generality of our implementation by applying it to Topaz, a Ruby VM, and Pycket, a Racket implementation.
Recently we introduced iron trichloride as an environmentally benign and cost-efficient reagent for the synthesis of N-benzoylguanidines. This highly attractive synthetic approach grants access to a broad spectrum of N-benzoylguanidines under mild conditions in short reaction times. In this work we present an extended scope of Our methodology along with the results obtained from mechanistic studies via in situ IR spectroscopy in combination with LC (liquid chromatography)-MS analyses. On the basis of these new mechanistic insights we were able to optimize the synthetic protocol and to develop an alternative mechanistic proposal. In this context the symbiotic roles of iron trithloride and oxygen in the guanylation process are highlighted.
Ionothermal carbon materials
(2016)
Alternative concepts for energy storage and conversion have to be developed, optimized and employed to fulfill the dream of a fossil-independent energy economy. Porous carbon materials play a major role in many energy-related devices. Among different characteristics, distinct porosity features, e.g., specific surface area (SSA), total pore volume (TPV), and the pore size distribution (PSD), are important to maximize the performance in the final device. In order to approach the aim to synthesize carbon materials with tailor-made porosity in a sustainable fashion, the present thesis focused on biomass-derived precursors employing and developing the ionothermal carbonization.
During the ionothermal carbonization, a salt melt simultaneously serves as solvent and porogen. Typically, eutectic mixtures containing zinc chloride are employed as salt phase. The first topic of the present thesis addressed the possibility to precisely tailor the porosity of ionothermal carbon materials by an experimentally simple variation of the molar composition of the binary salt mixture. The developed pore tuning tool allowed the synthesis of glucose derived carbon materials with predictable SSAs in the range of ~ 900 to ~ 2100 m2 g-1. Moreover, the nucleobase adenine was employed as precursor introducing nitrogen functionalities in the final material. Thereby, the chemical properties of the carbon materials are varied leading to new application fields. Nitrogen doped carbons (NDCs) are able to catalyze the oxygen reduction reaction (ORR) which takes place on the cathodic site of a fuel cell. The herein developed porosity tailoring allowed the synthesis of adenine derived NDCs with outstanding SSAs of up to 2900 m2 g-1 and very large TPV of 5.19 cm3 g-1. Furthermore, the influence of the porosity on the ORR could be directly investigated enabling the precise optimization of the porosity characteristics of NDCs for this application. The second topic addressed the development of a new method to investigate the not-yet unraveled mechanism of the oxygen reduction reaction using a rotating disc electrode setup. The focus was put on noble-metal free catalysts. The results showed that the reaction pathway of the investigated catalysts is pH-dependent indicating different active species at different pH-values. The third topic addressed the expansion of the used salts for the ionothermal approach towards hydrated calcium and magnesium chloride. It was shown that hydrated salt phases allowed the introduction of a secondary templating effect which was connected to the coexistence of liquid and solid salt phases. The method enabled the synthesis of fibrous NDCs with SSAs of up to 2780 m2 g-1 and very large TPV of 3.86 cm3 g-1. Moreover, the concept of active site implementation by a facile low-temperature metalation employing the obtained NDCs as solid ligands could be shown for the first time in the context of ORR.
Overall, the thesis may pave the way towards highly porous carbon with tailor-made porosity materials prepared by an inexpensive and sustainable pathway, which can be applied in energy related field thereby supporting the needed expansion of the renewable energy sector.
A combined dynamics consisting of Brownian motion and Levy flights is exhibited by a variety of biological systems performing search processes. Assessing the search reliability of ever locating the target and the search efficiency of doing so economically of such dynamics thus poses an important problem. Here we model this dynamics by a one-dimensional fractional Fokker-Planck equation combining unbiased Brownian motion and Levy flights. By solving this equation both analytically and numerically we show that the superposition of recurrent Brownian motion and Levy flights with stable exponent alpha < 1, by itself implying zero probability of hitting a point on a line, leads to transient motion with finite probability of hitting any point on the line. We present results for the exact dependence of the values of both the search reliability and the search efficiency on the distance between the starting and target positions as well as the choice of the scaling exponent a of the Levy flight component.
Abstract
By combining high-throughput sequencing with target enrichment (‘hybridization capture’), researchers are able to obtain molecular data from genomic regions of interest for projects that are otherwise constrained by sample quality (e.g. degraded and contamination-rich samples) or a lack of a priori sequence information (e.g. studies on nonmodel species). Despite the use of hybridization capture in various fields of research for many years, the impact of enrichment conditions on capture success is not yet thoroughly understood. We evaluated the impact of a key parameter – hybridization temperature – on the capture success of mitochondrial genomes across the carnivoran family Felidae. Capture was carried out for a range of sample types (fresh, archival, ancient) with varying levels of sequence divergence between bait and target (i.e. across a range of species) using pools of individually indexed libraries on Agilent SureSelect™ arrays. Our results suggest that hybridization capture protocols require specific optimization for the sample type that is being investigated. Hybridization temperature affected the proportion of on-target sequences following capture: for degraded samples, we obtained the best results with a hybridization temperature of 65 °C, while a touchdown approach (65 °C down to 50 °C) yielded the best results for fresh samples. Evaluation of capture performance at a regional scale (sliding window approach) revealed no significant improvement in the recovery of DNA fragments with high sequence divergence from the bait at any of the tested hybridization temperatures, suggesting that hybridization temperature may not be the critical parameter for the enrichment of divergent fragments.
Optical biosensors based on porous silicon were fabricated by metal assisted chemical etching. Thereby double layered porous silicon structures were obtained consisting of porous pillars with large pores on top of a porous silicon layer with smaller pores. These structures showed a similar sensing performance in comparison to electrochemically produced porous silicon interferometric sensors.
SOPARSE predicts so-called local coherence effects: locally plausible but globally impossible parses of substrings can exert a distracting influence during sentence processing. Additionally, it predicts digging-in effects: the longer the parser stays committed to a particular analysis, the harder it becomes to inhibit that analysis. We investigated the interaction of these two predictions using German sentences. Results from a self-paced reading study show that the processing difficulty caused by a local coherence can be reduced by first allowing the globally correct parse to become entrenched, which supports SOPARSE’s assumptions.
SOPARSE predicts so-called local coherence effects: locally plausible but globally impossible parses of substrings can exert a distracting influence during sentence processing. Additionally, it predicts digging-in effects: the longer the parser stays committed to a particular analysis, the harder it becomes to inhibit that analysis. We investigated the interaction of these two predictions using German sentences. Results from a self-paced reading study show that the processing difficulty caused by a local coherence can be reduced by first allowing the globally correct parse to become entrenched, which supports SOPARSE’s assumptions.
In a self-paced reading experiment, we investigated the processing of sluicing constructions ("sluices") whose antecedent contained a known garden path structure in German. Results showed decreased processing times for sluices with garden-path antecedents as well as a disadvantage for antecedents with non-canonical word order downstream from the ellipsis site. A post-hoc analysis showed the garden-path advantage also to be present in the region right before the ellipsis site. While no existing account of ellipsis processing explicitly predicted the results, we argue that they are best captured by combining a local antecedent mismatch effect with memory trace reactivation through reanalysis.
Filling the Silence
(2016)
In a self-paced reading experiment, we investigated the processing of sluicing constructions (“sluices”) whose antecedent contained a known garden-path structure in German. Results showed decreased processing times for sluices with garden-path antecedents as well as a disadvantage for antecedents with non-canonical word order downstream from the ellipsis site. A post-hoc analysis showed the garden-path advantage also to be present in the region right before the ellipsis site. While no existing account of ellipsis processing explicitly predicted the results, we argue that they are best captured by combining a local antecedent mismatch effect with memory trace reactivation through reanalysis.
Filling the Silence
(2016)
In a self-paced reading experiment, we investigated the processing of sluicing constructions (“sluices”) whose antecedent contained a known garden-path structure in German. Results showed decreased processing times for sluices with garden-path antecedents as well as a disadvantage for antecedents with non-canonical word order downstream from the ellipsis site. A post-hoc analysis showed the garden-path advantage also to be present in the region right before the ellipsis site. While no existing account of ellipsis processing explicitly predicted the results, we argue that they are best captured by combining a local antecedent mismatch effect with memory trace reactivation through reanalysis.
We investigate the influence of the Coriolis force on mass motion related to the Rheasilvia impact on asteroid Vesta. Observations by the NASA Dawn mission revealed a pattern of curved radial ridges, which are related to Coriolis-deflected mass-wasting during the initial modification stage of the crater. Utilizing the projected curvature of the mass-wasting trajectories, we developed a method that enabled investigation of the initial mass wasting of the Rheasilvia impact by observational means. We demonstrate that the Coriolis force can strongly affect the crater formation processes on rapidly rotating objects, and we derive the material's velocities (28.9 ± 22.5 m/s), viscosities (1.5–9.0 × 106 Pa s) and coefficients of friction (0.02–0.81) during the impact modification stage. The duration of the impact modification stage could be estimated to (1.1 ± 0.5) h. By analyzing the velocity distribution with respect to the topography, we deduce that the Rheasilvia impactor hit a heterogeneous target and that the initial crater walls were significantly steeper during the modification stage.
The increase in atmospheric methane concentration, which is determined by an imbalance between its sources and sinks, has led to investigations of the methane cycle in various environments. Aquatic environments are of an exceptional interest due to their active involvement in methane cycling worldwide and in particular in areas sensitive to climate change. Furthermore, being connected with each other aquatic environments form networks that can be spread on vast areas involving marine, freshwater and terrestrial ecosystems. Thus, aquatic systems have a high potential to translate local or regional environmental and subsequently ecosystem changes to a bigger scale. Many studies neglect this connectivity and focus on individual aquatic or terrestrial ecosystems.
The current study focuses on environmental controls of the distribution and aerobic oxidation of methane at the example of two aquatic ecosystems. These ecosystems are Arctic fresh water bodies and the Elbe estuary which represent interfaces between freshwater-terrestrial and freshwater-marine environments, respectively.
Arctic water bodies are significant atmospheric sources of methane. At the same time the methane cycle in Arctic water bodies is strongly affected by the surrounding permafrost environment, which is characterized by high amounts of organic carbon. The results of this thesis indicate that the methane concentrations in Arctic lakes and streams substantially vary between each other being regulated by local landscape features (e.g. floodplain area) and the morphology of the water bodies (lakes, streams and river). The highest methane concentrations were detected in the lake outlets and in a floodplain lake complex. In contrast, the methane concentrations measured at different sites of the Lena River did not vary substantially. The lake complexes in comparison to the Lena River, thus, appear as more individual and heterogeneous systems with a pronounced imprint of the surrounding soil environment. Furthermore, connected with each other Arctic aquatic environments have a large potential to transport methane from methane-rich water bodies such as streams and floodplain lakes to aquatic environments relatively poor in methane such as the Lena River.
Estuaries represent hot spots of oceanic methane emissions. Also, estuaries are intermediate zones between methane-rich river water and methane depleted marine water. Substantiated through this thesis at the example of the Elbe estuary, the methane distribution in estuaries, however, cannot entirely be described by the conservative mixing model i.e. gradual decrease from the freshwater end-member to the marine water end-member. In addition to the methane-rich water from the Elbe River mouth substantial methane input occurs from tidal flats, areas of significant interaction between aquatic and terrestrial environments. Thus, this study demonstrates the complex interactions and their consequences for the methane distribution within estuaries. Also it reveals how important it is to investigate estuaries at larger spatial scales.
Methane oxidation (MOX) rates are commonly correlated with methane concentrations. This was shown in previous research studies and was substantiated by the present thesis. In detail, the highest MOX rates in the Arctic water bodies were detected in methane-rich streams and in the floodplain area while in the Elbe estuary the highest MOX rates were observed at the coastal stations. However, in these bordering environments, MOX rates are affected not only via the regulation through methane concentrations. The MOX rates in the Arctic lakes were shown to be also dependent on the abundance and community composition of methane-oxidising bacteria (MOB), that in turn are controlled by local landscape features (regardless of the methane concentrations) and by the transport of MOB between neighbouring environments. In the Elbe estuary, the MOX rates in addition to the methane concentrations are largely affected by the salinity, which is in turn regulated by the mixing of fresh- and marine waters. The magnitude of the salinity impact on MOX rates thereby depends on the MOB community composition and on the rate of the salinity change.
This study extends our knowledge of environmental controls of methane distribution and aerobic methane oxidation in aquatic environments. It also illustrates how important it is to investigate complex ecosystems rather than individual ecosystems to better understand the functioning of whole biomes.
Boolean networks (and more general logic models) are useful frameworks to study signal transduction across multiple pathways. Logic models can be learned from a prior knowledge network structure and multiplex phosphoproteomics data. However, most efficient and scalable training methods focus on the comparison of two time-points and assume that the system has reached an early steady state. In this paper, we generalize such a learning procedure to take into account the time series traces of phosphoproteomics data in order to discriminate Boolean networks according to their transient dynamics. To that end, we identify a necessary condition that must be satisfied by the dynamics of a Boolean network to be consistent with a discretized time series trace. Based on this condition, we use Answer Set Programming to compute an over-approximation of the set of Boolean networks which fit best with experimental data and provide the corresponding encodings. Combined with model-checking approaches, we end up with a global learning algorithm. Our approach is able to learn logic models with a true positive rate higher than 78% in two case studies of mammalian signaling networks; for a larger case study, our method provides optimal answers after 7 min of computation. We quantified the gain in our method predictions precision compared to learning approaches based on static data. Finally, as an application, our method proposes erroneous time-points in the time series data with respect to the optimal learned logic models. (C) 2016 Elsevier Ireland Ltd. All rights reserved.
Massive stars are extremely luminous and drive strong winds, blowing a large part of their matter into the galactic environment before they finally explode as a supernova. Quantitative knowledge of massive star feedback is required to understand our Universe as we see it. Traditionally, massive stars have been studied under the assumption that their winds are homogeneous and stationary, largely relying on the Sobolev approximation. However, Observations with the newest instruments, together with progress in model calculations, ultimately dictate a cardinal change of this paradigm: stellar winds are highly inhomogeneous. Hence, we are now advancing to a new stage in our understanding of stellar winds. Using the foundations laid by V.V. Sobolev and his school, we now update and further develop the stellar spectral analysis techniques. New sophisticated 3-D models of radiation transfer in inhomogeneous expanding media elucidate the physics of stellar winds and improve classical empiric mass-loss rate diagnostics. Applications of these new techniques to multiwavelength observations of massive stars yield consistent and robust stellar wind parameters. (C) 2016 Elsevier Ltd. All rights reserved.
Nearly all types of massive stars with radiatively driven stellar winds are X-ray sources that can be observed by the presently operating powerful X-ray telescopes. In this review I briefly address recent advances in our understanding of stellar winds obtained from X-ray observations. X-rays may strongly influence the dynamics of weak winds of main sequence B-type stars. X-ray pulsations were detected in a beta Cep type variable giving evidence of tight photosphere-wind connections. The winds of OB dwarfs with subtypes later than O9V may be predominantly in a hot phase, and X-ray observations offer the best window for their studies. The X-ray properties of OB super giants are largely determined by the effects of radiative transfer in their clumped stellar winds. The recently suggested method to directly measure mass-loss rates of O stars by fitting the shapes of X-ray emission lines is considered but its validity cannot be confirmed. To obtain robust quantitative information on stellar wind parameters from X-ray spectroscopy, a multiwavelength analysis by means of stellar atmosphere models is required. Independent groups are now performing such analyses with encouraging results. Joint analyses of optical, UV, and X-ray spectra of OB supergiants yield consistent mass-loss rates. Depending on the adopted clumping parameters, the empirically derived mass-loss rates are a factor of a few smaller or comparable to those predicted by standard recipes (Vink et al., 2001). All sufficiently studied O stars display variable X-ray emission that might be related to corotating interaction regions in their winds. In the latest stages of stellar evolution, single red supergiants (RSG) and luminous blue variable (LBV) stars do not emit observable amounts of X-rays. On the other hand, nearly all types of Wolf-Rayet (WR) stars are X-ray sources. X-ray spectroscopy allows a sensitive probe of WR wind abundances and opacities. (C) 2016 COSPAR. Published by Elsevier Ltd. All rights reserved.
We conduct experiments based on the oligopoly model by Kreps and Scheinkman (1983) to assess the impact of demand side concentration on market outcomes. Both buyers and sellers in our markets are humans. The number of firms is fixed at three in all treatments. Only the number of buyers is varied and total demand is split equally among them. We observe that firms set lower prices in markets with only few buyers, namely one or two. Price dispersion is higher in markets with few buyers. Aggregate demand withholding decreases with the number of buyers. This results in lower profits for firms and higher profits for buyers in markets with few buyers. (C) 2015 Elsevier B.V. All rights reserved.
I examine the determinants of both perceived inflation and unemployment in one single survey and include Big Five traits in the analysis. This is the first survey on this topic in Germany. My sample consists of 1771 students from different fields and levels. Using PhD students’ estimates as a reference, I create categories for underestimation and overestimation of both variables. Multinomial logit regressions show that females overestimate both variables. Education and news consumption reduce misestimation. A higher level of Neuroticism is related with a higher probability to overestimate unemployment. Overstating (understating) one indicator is associated with overstating (understating) the other.
Tubers of potato (Solanum tuberosum L.), one of the most important crops, are a prominent example for an efficient production of storage starch. Nevertheless, the synthesis of this storage starch is not completely understood. The plastidial phosphorylase (Phol; EC 2.4.11) catalyzes the reversible transfer of glucosyl residues from glucose-1-phosphate to the non-reducing end of alpha-glucans with the release of orthophosphate. Thus, the enzyme is in principle able to act during starch synthesis. However, so far under normal growth conditions no alterations in tuber starch metabolism were observed. Based on analyses of other species and also from in vitro experiments with potato tuber slices it was supposed, that Phol has a stronger impact on starch metabolism, when plants grow under low temperature conditions. Therefore, we analyzed the starch content, granule size, as well as the internal structure of starch granules isolated from potato plants grown under low temperatures. Besides wild type, transgenic potato plants with a strong reduction in the Phol activity were analyzed. No significant alterations in starch content and granule size were detected. In contrast, when plants were cultivated at low temperatures the chain length distributions of the starch granules were altered. Thus, the granules contained more short glucan chains. That was not observed in the transgenic plants, revealing that Pho1 in wild type is involved in the formation of the short glucan chains, at least at low temperatures. (C) 2016 Elsevier Masson SAS. All rights reserved.
Faktor Mensch
(2016)
Eine Krisensituation ist eine Umbruchssituation. Sie kann als Chance, als Herausforderung sowie im Sinne einer SCHUMPETER’SCHEN „schöpferischen Zerstörung“ als Ausgangspunkt von bedeutsamen Veränderungen und neuen Entwicklungsmöglichkeiten begriffen werden. Die Krisensituation der 1970er und 1980er Jahre bildet dahingehend durch ihre Einzigartigkeit einen herausragenden wirtschaftshistorischen Untersuchungsgegenstand. Für die westeuropäischen Staaten waren es nicht nur Jahre einer, nach der außergewöhnlich langen Boomzeit der „Wirtschaftswunderjahre“, problematischen sozialen und wirtschaftliche Situation. Es war auch eine Zeit eines bedeutungsvollen und beschleunigten Wandels. Die Gleichzeitigkeit vieler Veränderungen, das zeitliche Zusammentreffen von konjunkturellen und strukturellen Problemlagen sowie die äußerst kritische Situation an den westeuropäischen Arbeitsmärkten bildete eine multiple Krisensituation. Deren Auswirkungen waren weitreichender, als es von den Zeitgenossen erahnt werden konnte. Es gab nicht nur Änderungen im (wirtschafts-)politischen Makrogefüge vieler Volkswirtschaften, auch bedeutende Einflüsse waren auf der Mikroebene feststellbar. Marktorientierte Unternehmen mussten sich auf die neue Situation einstellen und im Rahmen einer Neupositionierung von Betriebsstrategien, organisatorischen Umgestaltungen und einer stärkeren Ressourcenorientierung betriebswirtschaftlich handeln. Das schien letztlich zu einer stärkeren Beachtung und Entwicklung der in den Unternehmen vorhandenen humanen und sozialen Ressourcen zu führen.
Diese Arbeit stellt die Hypothese auf, dass umfassende organisatorische Veränderungen und strategische Neupositionierungen, insbesondere die effektivere Nutzung sowie der intensive Auf- und Ausbau betriebsinterner Personalressourcen Unternehmen maßgeblich halfen, die Krisensituation der 1970er und 1980er Jahre besser und nachhaltiger überwinden zu können. Anders als die bisherige wirtschaftshistorische Forschungsliteratur nimmt diese Dissertation nicht die makroökonomisch Perspektive in den Fokus, sondern untersucht die Hypothese anhand mehrerer Unternehmensfallstudien. Ausgewählt sind drei Großunternehmen der westeuropäischen Elektroindustrie. Diese Arbeit liefert mit dieser Untersuchung einen weiteren Baustein zur wirtschaftshistorischen Annäherung an die 1970er und 1980er Jahre und leistet ebenso einen Beitrag zur Fortschreibung der Firmengeschichte der drei Unternehmen.
Die Elektrobranche fand bisher wirtschaftshistorisch nur wenig Beachtung, dennoch ist sie ein gutes Beispiel für die umfassende Veränderungssituation jener Jahre. Entsprechende Sekundärquellen sind für diesen Zeitraum für die drei Unternehmen kaum vorhanden. Aus diesem Grund bildet eine Vielzahl von Archivalien das Fundament dieser Arbeit. Sie werden als Primärquellen aus den jeweiligen Unternehmensarchiven als Basis der Fallanalyse herangezogen. Mit Hilfe zahlreicher Dokumente des betrieblichen „Alltagsgeschäfts“, wie beispielsweise Daten des betrieblichen Personal- und Rechnungswesens, Protokolle von Sitzungen der Arbeitsnehmervertreter, des Aufsichtsrats oder des Vorstands sowie interne Strategiepapiere und Statistiken, wird nicht nur der anfangs aufgestellten Hypothese nachgegangen, sondern auch mehrerer sich aus ihr ergebende Fragenkomplexe. Im Rahmen derer wird untersucht, wie die Unternehmen – die Beschäftigten, die Leitungsebenen und die Aufsichtsräte – auf die Krisensituation reagierten, ob sie ggf. ihrerseits Einfluss darauf zu nehmen versuchten und welche betriebswirtschaftlichen Schlüsse daraus gezogen wurden. Es wird hinterfragt, ob eine stärkere Ressourcenorientierung wirklich eine neue Strategieperspektive bot und es diesbezüglich zu einer stärkeren Beachtung humaner und sozialer Ressourcen im Unternehmen kam. Diese Arbeit untersucht, ob gezielt zur Krisenüberwindung in diese Ressourcen investiert wurde und diese Investitionen halfen, die Krisensituation erfolgreich zu überstehen und nachhaltig den Unternehmenserfolg zu sichern.
Using density functional theory (PBE functional), we show that the degree of surface hydroxylation increases in the MgO, CaO, SrO series, accompanied by an increase in water adsorption energy. Already for water coverage of two monolayers, structures with dissolved M2+. ions are considerably more stable than the intact, nondissolved surface. The dissolved ions above the surface form different patterns including ordered ones (e.g., an infinite stripe) that are preferred for MgO(001) and CaO(001) and disordered ones that are favored for SrO(001). Contrary to previous assignments, an analysis of calculated X-ray photoelectron spectra shows that O(1s) signals arising from OH and H2O groups might coincide in the experimental spectrum.
Devising computational methods to accurately reconstruct gene regulatory networks given gene expression data is key to systems biology applications. Here we propose a method for reconstructing gene regulatory networks by simultaneous consideration of data sets from different perturbation experiments and corresponding controls. The method imposes three biologically meaningful constraints: (1) expression levels of each gene should be explained by the expression levels of a small number of transcription factor coding genes, (2) networks inferred from different data sets should be similar with respect to the type and number of regulatory interactions, and (3) relationships between genes which exhibit similar differential behavior over the considered perturbations should be favored. We demonstrate that these constraints can be transformed in a fused LASSO formulation for the proposed method. The comparative analysis on transcriptomics time-series data from prokaryotic species, Escherichia coli and Mycobacterium tuberculosis, as well as a eukaryotic species, mouse, demonstrated that the proposed method has the advantages of the most recent approaches for regulatory network inference, while obtaining better performance and assigning higher scores to the true regulatory links. The study indicates that the combination of sparse regression techniques with other biologically meaningful constraints is a promising framework for gene regulatory network reconstructions.
Toxic Cr(III) which poses environmental hazard to flora and fauna was efficiently abstracted by low-cost Nauclea diderrichii seed biomass (NDS) with good sequestral capacity for this metal was investigated in this study. The NDS surface analyses showed that it has a specific surface area of 5.36 m(2)/g and pHpzc of 4.90. Thermogravimetric analysis of NDS showed three consecutive weight losses from 50-200 degrees C (ca. 5%), 200-400 C (ca. 35%), >400 degrees C (ca. 10%), corresponding to external water molecules, structural water molecules and heat induced condensation reactions respectively. Differential thermogram of NDS presented a large endothermic peak between 20-510 degrees C suggesting bond breakage and dissociation with the ultimate release of small molecules. The experimental data showed kinetically fast biosorption with increased initial Cr(III) concentrations, indicating the role of external mass transfer mechanism as the rate controlling mechanism in this adsorption process. The Langmuir biosorption capacity of NDS was 483.81 mg/g. The use of the corrected Akaike Information Criterion tool for ranking equilibrium models suggested that the Freundlich model best described the experimental data, which is an indication of the heterogeneous nature of the active sites on the surface of NDS. N. diderrichii seed biomass is an easily sourced, cheap and environmental friendly biosorbent which will serve as a good and cost effective alternative to activated carbon for the treatment of polluted water and industrial effluents. (C) 2012 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.
The competitive extraction of Cr(III) onto Nauclea diderrichii seed epicarp doped with MnO2 nanoparticles (MnO2 nano-bioextractant (MNB)) in a single and binary batch system was studied. For validity of experimental data, chi square test, root mean square error, sum of the square errors, hybrid fractional error function, Marquart’s percent standard deviation and standard absolute error were used. Among the kinetic models used, pseudo-second-order and Langmuir equations gave the best fits for the experimental data, with qe (mg g) for the uptake of Cr(III) in single metal system onto MNB, then Cr(III) with Cd(II), Pb(II), Hg(II), KCl and CaCl2 in binary metal systems onto MNB were 2.611, then 1.989, 1.016, 2.208, 1.249 and 1.868 from kinetic standpoint, respectively. The initial sorption rates, h (mg/g/min), and half lives, t1/2 (min), for the uptake of Cr(III) in single metal system onto MNB, then Cr(III) with Cd(II), Pb(II), Hg(II), KCl and CaCl2 in binary metal system onto MNB were 3.497, then 2.311, 2.274, 0.242, 2.956, 45.568 and 0.747, then 5.769, 1.766, 12.144, 1.762, and 2.415, respectively. Physicochemical surface analyses such as pH of point of zero charge, Brunauer–Emmett–Teller single point and multi-point techniques for surface area analyses, scanning electron microscopy and transmission electron microscopy were done on MNB and MnO2 nanoparticles in order to understand their surface microstructures. Desorption study showed that MNB can be recycled and used for future study. Hence, MNB showed good potential to remediate Cr(III) from wastewaters and polluted water.
The energy sector is both affected by climate change and a key sector for climate protection measures. Energy security is the backbone of our modern society and guarantees the functioning of most critical infrastructure. Thus, decision makers and energy suppliers of different countries should be familiar with the factors that increase or decrease the susceptibility of their electricity sector to climate change. Susceptibility means socioeconomic and structural characteristics of the electricity sector that affect the demand for and supply of electricity under climate change. Moreover, the relevant stakeholders are supposed to know whether the given national energy and climate targets are feasible and what needs to be done in order to meet these targets. In this regard, a focus should be on the residential building sector as it is one of the largest energy consumers and therefore emitters of anthropogenic CO 2 worldwide.
This dissertation addresses the first aspect, namely the susceptibility of the electricity sector, by developing a ranked index which allows for quantitative comparison of the electricity sector susceptibility of 21 European countries based on 14 influencing factors. Such a ranking has not been completed to date. We applied a sensitivity analysis to test the relative effect of each influencing factor on the susceptibility index ranking. We also discuss reasons for the ranking position and thus the susceptibility of selected countries. The second objective, namely the impact of climate change on the energy demand of buildings, is tackled by means of a new model with which the heating and cooling energy demand of residential buildings can be estimated. We exemplarily applied the model to Germany and the Netherlands. It considers projections of future changes in population, climate and the insulation standards of buildings, whereas most of the existing studies only take into account fewer than three different factors that influence the future energy demand of buildings. Furthermore, we developed a comprehensive retrofitting algorithm with which the total residential building stock can be modeled for the first time for each year in the past and future.
The study confirms that there is no correlation between the geographical location of a country and its position in the electricity sector susceptibility ranking. Moreover, we found no pronounced pattern of susceptibility influencing factors between countries that ranked higher or lower in the index. We illustrate that Luxembourg, Greece, Slovakia and Italy are the countries with the highest electricity sector susceptibility. The electricity sectors of Norway, the Czech Republic, Portugal and Denmark were found to be least susceptible to climate change. Knowledge about the most important factors for the poor and good ranking positions of these countries is crucial for finding adequate adaptation measures to reduce the susceptibility of the electricity sector. Therefore, these factors are described within this study.
We show that the heating energy demand of residential buildings will strongly decrease in both Germany and the Netherlands in the future. The analysis for the Netherlands focused on the regional level and a finer temporal resolution which revealed strong variations in the future heating energy demand changes by province and by month. In the German study, we additionally investigated the future cooling energy demand and could demonstrate that it will only slightly increase up to the middle of this century. Thus, increases in the cooling energy demand are not expected to offset reductions in heating energy demand. The main factor for substantial heating energy demand reductions is the retrofitting of buildings. We are the first to show that the given German and Dutch energy and climate targets in the building sector can only be met if the annual retrofitting rates are substantially increased. The current rate of only about 1 % of the total building stock per year is insufficient for reaching a nearly zero-energy demand of all residential buildings by the middle of this century. To reach this target, it would need to be at least tripled. To sum up, this thesis emphasizes that country-specific characteristics are decisive for the electricity sector susceptibility of European countries. It also shows for different scenarios how much energy is needed in the future to heat and cool residential buildings. With this information, existing climate mitigation and adaptation measures can be justified or new actions encouraged.
La siguiente investigación aborda la relación entre mito y modernidad en la obra literaria (poemas, cuentos, novelas y crónicas) del autor chileno Rosamel del Valle (Curacaví, 1901 – Santiago de Chile, 1965). En sus distintos textos existe una tensión entre un proyecto poético basado en una visión mítica del mundo y un contexto histórico que privilegia posturas más racionalistas, relegando lo poético y lo mítico. Ya en el siglo XIX la modernidad y los fenómenos asociados de la modernización producen el desplazamiento de la poesía como discurso y del poeta como persona a una situación deficitaria dentro de la sociedad, lo que se extiende en el siglo XX. Debido a este conflicto Rosamel del Valle cuestiona en su obra los alcances de sus propios postulados, tanto estéticos como vitales. Esto conlleva una vacilación entre la reafirmación de su proyecto poético-vital y la consciencia del fracaso. Es por esto que la obra del poeta chileno contiene un Lebenswissen, que concibe a la poesía como una forma privilegiada de vida. Sin embargo, debido a las dificultades de las condiciones históricas es posible entender este Lebenswissen también como un ÜberLebenswissen (Ette).
En la primera parte del texto se estudia la concepción mítica de la poesía de del Valle y se analiza los distintos niveles en los que aparece el mito en su obra literaria: como pensamiento, como lenguaje y como narración tradicional. La identificación de la poesía como mito muestra las principales características de la poética de del Valle: una concepción ontológica que diferencia entre una dimensión visible y otra invisible de la realidad; la tendencia mística de la poesía; una concepción cíclica del tiempo que funda una relación con los discursos de la memoria y de la muerte, así como la idea de un pasado utópico que por medio de la poesía podría revivir en el presente; además de la figura de la mujer cómo símbolo del amor y de la poesía.
En la segunda parte se investiga la relación y las consecuencias de esta “poesía mítica” en el contexto de la modernidad. Se aborda especialmente el efecto en la poética de Rosamel del Valle de la Entzauberung der Welt (Weber), como experiencia específica de la época. Para esto se destaca ante todo sus impresiones sobre Nueva York. Esta ciudad en la que vivió y trabajó entre 1946 y 1963, se transforma en sus textos en un lugar en el que sería posible el “habitar poético del hombre” en la modernidad.
Vegetation has long been hypothesized to influence the nature and rates of surface processes. We test the possible impact of vegetation and climate on denudation rates at orogen scale by taking advantage of a pronounced along-strike gradient in rainfall and vegetation density in the Himalaya. We combine 12 new Be-10 denudation rates from the Sutlej Valley and 123 published denudation rates from fluvially-dominated catchments in the Himalaya with remotely-sensed measures of vegetation density and rainfall metrics, and with tectonic and lithologic constraints. In addition, we perform topographic analyses to assess the contribution of vegetation and climate in modulating denudation rates along strike. We observe variations in denudation rates and the relationship between denudation and topography along strike that are most strongly controlled by local rainfall amount and vegetation density, and cannot be explained by along-strike differences in tectonics or lithology. A W-E along-strike decrease in denudation rate variability positively correlates with the seasonality of vegetation density (R = 0.95, p < 0.05), and negatively correlates with mean vegetation density (R = -0.84, p < 0.05). Vegetation density modulates the topographic response to changing denudation rates, such that the functional relationship between denudation rate and topographic steepness becomes increasingly linear as vegetation density increases. We suggest that while tectonic processes locally control the pattern of denudation rates across strike of the Himalaya (i.e., S-N), along strike of the orogen (i.e., E-W) climate exerts a measurable influence on how denudation rates scatter around long-term, tectonically-controlled erosion, and on the functional relationship between topography and denudation. (C) 2016 Elsevier B.V. All rights reserved.
Understanding the rates and processes of denudation is key to unraveling the dynamic processes that shape active orogens. This includes decoding the roles of tectonic and climate-driven processes in the long-term evolution of high- mountain landscapes in regions with pronounced tectonic activity and steep climatic and surface-process gradients. Well-constrained denudation rates can be used to address a wide range of geologic problems. In steady-state landscapes, denudation rates are argued to be proportional to tectonic or isostatic uplift rates and provide valuable insight into the tectonic regimes underlying surface denudation. The use of denudation rates based on terrestrial cosmogenic nuclide (TCN) such as 10Beryllium has become a widely-used method to quantify catchment-mean denudation rates. Because such measurements are averaged over timescales of 102 to 105 years, they are not as susceptible to stochastic changes as shorter-term denudation rate estimates (e.g., from suspended sediment measurements) and are therefore considered more reliable for a comparison to long-term processes that operate on geologic timescales. However, the impact of various climatic, biotic, and surface processes on 10Be concentrations and the resultant denudation rates remains unclear and is subject to ongoing discussion. In this thesis, I explore the interaction of climate, the biosphere, topography, and geology in forcing and modulating denudation rates on catchment to orogen scales.
There are many processes in highly dynamic active orogens that may effect 10Be concentrations in modern river sands and therefore impact 10Be-derived denudation rates. The calculation of denudation rates from 10Be concentrations, however, requires a suite of simplifying assumptions that may not be valid or applicable in many orogens. I investigate how these processes affect 10Be concentrations in the Arun Valley of Eastern Nepal using 34 new 10Be measurements from the main stem Arun River and its tributaries. The Arun Valley is characterized by steep gradients in climate and topography, with elevations ranging from <100 m asl in the foreland basin to >8,000 asl in the high sectors to the north. This is coupled with a five-fold increase in mean annual rainfall across strike of the orogen. Denudation rates from tributary samples increase toward the core of the orogen, from <0.2 to >5 mm/yr from the Lesser to Higher Himalaya. Very high denudation rates (>2 mm/yr), however, are likely the result of 10Be TCN dilution by surface and climatic processes, such as large landsliding and glaciation, and thus may not be representative of long-term denudation rates. Mainstem Arun denudation rates increase downstream from ~0.2 mm/yr at the border with Tibet to 0.91 mm/yr at its outlet into the Sapt Kosi. However, the downstream 10Be concentrations may not be representative of the entire upstream catchment. Instead, I document evidence for downstream fining of grains from the Tibetan Plateau, resulting in an order-of-magnitude apparent decrease in the measured 10Be concentration.
In the Arun Valley and across the Himalaya, topography, climate, and vegetation are strongly interrelated. The observed increase in denudation rates at the transition from the Lesser to Higher Himalaya corresponds to abrupt increases in elevation, hillslope gradient, and mean annual rainfall. Thus, across strike (N-S), it is difficult to decipher the potential impacts of climate and vegetation cover on denudation rates. To further evaluate these relationships I instead took advantage of an along-strike west-to-east increase of mean annual rainfall and vegetation density in the Himalaya. An analysis of 136 published 10Be denudation rates from along strike of the revealed that median denudation rates do not vary considerably along strike of the Himalaya, ~1500 km E-W. However, the range of denudation rates generally decreases from west to east, with more variable denudation rates in the northwestern regions of the orogen than in the eastern regions. This denudation rate variability decreases as vegetation density increases (R=- 0.90), and increases proportionately to the annual seasonality of vegetation (R=0.99). Moreover, rainfall and vegetation modulate the relationship between topographic steepness and denudation rates such that in the wet, densely vegetated regions of the Himalaya, topography responds more linearly to changes in denudation rates than in dry, sparsely vegetated regions, where the response of topographic steepness to denudation rates is highly nonlinear. Understanding the relationships between denudation rates, topography, and climate is also critical for interpreting sedimentary archives. However, there is a lack of understanding of how terrestrial organic matter is transported out of orogens and into sedimentary archives. Plant wax lipid biomarkers derived from terrestrial and marine sedimentary records are commonly used as paleo- hydrologic proxy to help elucidate these problems. I address the issue of how to interpret the biomarker record by using the plant wax isotopic composition of modern suspended and riverbank organic matter to identify and quantify organic matter source regions in the Arun Valley. Topographic and geomorphic analysis, provided by the 10Be catchment-mean denudation rates, reveals that a combination of topographic steepness (as a proxy for denudation) and vegetation density is required to capture organic matter sourcing in the Arun River.
My studies highlight the importance of a rigorous and careful interpretation of denudation rates in tectonically active orogens that are furthermore characterized by strong climatic and biotic gradients. Unambiguous information about these issues is critical for correctly decoding and interpreting the possible tectonic and climatic forces that drive erosion and denudation, and the manifestation of the erosion products in sedimentary archives.
The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using Förster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.
The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using Förster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.
The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using Forster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.
During visual fixation, the eye generates microsaccades and slower components of fixational eye movements that are part of the visual processing strategy in humans. Here, we show that ongoing heartbeat is coupled to temporal rate variations in the generation of microsaccades. Using coregistration of eye recording and ECG in humans, we tested the hypothesis that microsaccade onsets are coupled to the relative phase of the R-R intervals in heartbeats. We observed significantly more microsaccades during the early phase after the R peak in the ECG. This form of coupling between heartbeat and eye movements was substantiated by the additional finding of a coupling between heart phase and motion activity in slow fixational eye movements; i.e., retinal image slip caused by physiological drift. Our findings therefore demonstrate a coupling of the oculomotor system and ongoing heartbeat, which provides further evidence for bodily influences on visuomotor functioning.
Saccadic eye movements are frequently followed by smaller secondary saccades which are generally assumed to correct for the error in primary saccade landing position. However, secondary saccades can also occur after accurate primary saccades and they are often as small as microsaccades, therefore raising the need to further scrutinize the processes involved in secondary saccade generation. Following up a previous study, we analyzed secondary saccades using rate analysis which allows us to quantify experimental effects as shifts in distributions, therefore going beyond comparisons of mean differences. We use Aalen’s additive hazards model to delineate the time course of key influences on the secondary saccade rate. In addition to the established effect of primary saccade error, we observed a time-varying influence of under- vs. overshooting – with a higher risk of generating secondary saccades following undershoots. Moreover, increasing target eccentricity influenced the programming of secondary saccades, therefore demonstrating that error-unrelated variables co-determine secondary saccade programs. Our results provide new insights into the generative mechanisms of small saccades during postsaccadic fixation that need to be accounted for by secondary saccade models.
Self-assembling biomolecules provide attractive templates for the preparation of metallic nanostructures. However, the intuitive transfer of the "outer shape" of the assembled macromolecules to the final metallic particle depends on the intermolecular forces among the biomolecules which compete with interactions between template molecules and the metal during metallization. The shape of the bio-template may thus be more dynamic than generally assumed. Here, we have studied the metallization of phospholipid nanodiscs which are discoidal particles of similar to 10 nm diameter containing a lipid bilayer similar to 5 nm thick. Using negatively charged lipids, electrostatic adsorption of amine-coated Au nanoparticles was achieved and followed by electroless gold deposition. Whereas Au nanoparticle adsorption preserves the shape of the bio-template, metallization proceeds via invasion of Au into the hydrophobic core of the nanodisc. Thereby, the lipidic phase induces a lateral growth that increases the diameter but not the original thickness of the template. Infrared spectroscopy reveals lipid expansion and suggests the existence of internal gaps in the metallized nanodiscs, which is confirmed by surface-enhanced Raman scattering from the encapsulated lipids. Interference of metallic growth with non-covalent interactions can thus become itself a shape-determining factor in the metallization of particularly soft and structurally anisotropic biomaterials.
Ice-rich permafrost coasts often undergo rapid erosion, which results in land loss and release of considerable amounts of sediment, organic carbon and nutrients, impacting the near-shore ecosystems. Because of the lack of volumetric erosion data, Arctic coastal erosion studies typically report on planimetric erosion. Our aim is to explore the relationship between planimetric and volumetric coastal erosion measurements and to update the coastal erosion rates on Herschel Island in the Canadian Arctic. We used high-resolution digital elevation models to compute sediment release and compare volumetric data to planimetric estimations of coastline movements digitized from satellite imagery. Our results show that volumetric erosion is locally less variable and likely corresponds better with environmental forcing than planimetric erosion. Average sediment release volumes are in the same range as sediment release volumes calculated from coastline movements combined with cliff height. However, the differences between these estimates are significant for small coastal sections. We attribute the differences between planimetric and volumetric coastal erosion measurements to mass wasting, which is abundant along the coasts of Herschel Island. The average recorded coastline retreat on Herschel Island was 0.68m a(-1) for the period 2000-2011. Erosion rates increased by more than 50% in comparison with the period 1970-2000, which is in accordance with a recently observed increase along the Alaskan Beaufort Sea. The estimated annual sediment release was 28.2 m(3) m(-1) with resulting fluxes of 590 kg C m(-1) and 104 kg N m(-1).