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Ausgehend von der typischen IT‐Infrastruktur für E‐Learning an Hochschulen auf der einen Seite sowie vom bisherigen Stand der Forschung zu Personal Learning Environments (PLEs) auf der anderen Seite zeigt dieser Beitrag auf, wie bestehende Werkzeuge bzw. Dienste zusammengeführt und für die Anforderungen der modernen, rechnergestützten Präsenzlehre aufbereitet werden können. Für diesen interdisziplinären Entwicklungsprozess bieten sowohl klassische Softwareentwicklungsverfahren als auch bestehende PLE‐Modelle wenig Hilfestellung an. Der Beitrag beschreibt die in einem campusweiten Projekt an der Universität Potsdam verfolgten Ansätze und die damit erzielten Ergebnisse. Dafür werden zunächst typische Lehr‐/Lern‐bzw. Kommunikations‐Szenarien identifiziert, aus denen Anforderungen an eine unterstützende Plattform abgeleitet werden. Dies führt zu einer umfassenden Sammlung zu berücksichtigender Dienste und deren Funktionen, die gemäß den Spezifika ihrer Nutzung in ein Gesamtsystem zu integrieren sind. Auf dieser Basis werden grundsätzliche Integrationsansätze und technische Details dieses Mash‐Ups in einer Gesamtschau aller relevanten Dienste betrachtet und in eine integrierende Systemarchitektur überführt. Deren konkrete Realisierung mit Hilfe der Portal‐Technologie Liferay wird dargestellt, wobei die eingangs definierten Szenarien aufgegriffen und exemplarisch vorgestellt werden. Ergänzende Anpassungen im Sinne einer personalisierbaren bzw. adaptiven Lern‐(und Arbeits‐)Umgebung werden ebenfalls unterstützt und kurz aufgezeigt.
Dispersion engineered silicon nitride waveguides by geometrical and refractive-index optimization
(2014)
Dispersion engineering in silicon nitride (SiXNY) waveguides is investigated through the optimization of the waveguide transversal dimensions and refractive indices in a multicladding arrangement. Ultraflat dispersion of -84.0 +/- 0.5 ps/nm/km between 1700 and 2440 nm and 1.5 +/- 3 ps/nm/km between 1670 and 2500 nm is numerically demonstrated. It is shown that typical refractive index fluctuations as well as dimension fluctuations during fabrication of the SiXNY waveguides are a limitation for obtaining ultraflat dispersion profiles. Single- and multicladding waveguides are fabricated and their dispersion profiles measured (over nearly 1000 nm) using a low-coherence frequency domain interferometric technique. By appropriate thickness optimization, the zero-dispersion wavelength is tuned over a large spectral range in single-and multicladding waveguides with small refractive index contrast (3%). A flat dispersion profile with +/- 3.2 ps/nm/km variation over 500 nm is obtained in a multicladding waveguide fabricated with a refractive index contrast of 37%. Finally, we generate a nearly three-octave supercontinuum in this dispersion flattened multicladding SiXNY waveguide. (C) 2014 Optical Society of America
Until now, spatially resolved Raman Spectroscopy has required to scan a sample under investigation in a time-consuming step-by-step procedure. Here, we present a technique that allows the capture of an entire Raman image with only one single exposure. The Raman scattering arising from the sample was collected with a fiber-coupled high-performance astronomy spectrograph. The probe head consisting of an array of 20 x 20 multimode fibers was linked to the camera port of a microscope. To demonstrate the high potential of this new concept, Raman images of reference samples were recorded. Entire chemical maps were received without the need for a scanning procedure.
Der vorliegende Text gibt eine Bestandserhebung der bisher stattgefundenen Aktivitäten im E-Learning an der Universität Potsdam wieder, andererseits dient er auch dazu, Potenziale zu sichten und in einem nächstem Schritt daraus Ideen und Vorschläge für eine hochschulweite E-Learning-Strategie abzuleiten. Zielsetzung der Bestandsaufnahme ist es, die relevanten Informationen darzustellen, über den Platz der Universität Potsdam in der hochschulischen E-Learning-Landschaft zu orientieren und den Stand der Entwicklung zu bewerten.
Von Ulfila bis Rekkared
(2014)
Für etwa 200 Jahre, vom Ende des 4. Jahrhunderts bis 589 n. Chr., gehören die Westgoten einem von der Orthodoxie der Reichskirche abweichenden christlichen Bekenntnis an. Auf dem 3. Konzil von Toledo beendet König Rekkared diesen Zustand religiöser Alterität durch die Konversion zum Katholizismus. Die antiken Berichte zeichnen nur vordergründig ein kohärentes Bild des Christentums der Goten. Dagegen weist Eike Faber Widersprüche und Fehler in der Überlieferung nach und bietet eine Reihe neuer Interpretationen an. Die genauere Betrachtung vermag dabei sowohl den dogmatischen Gehalt des Christentums der Goten schärfer zu konturieren als auch die Beweggründe für die Annahme des neuen Glaubens herauszustellen und die traditionelle Datierung dieses Vorgangs zu widerlegen. Schließlich wird deutlich, welche Funktion das fortgesetzte Festhalten an einer demonstrativ anderen religiösen Überzeugung für die Goten hatte. Prägnante Wegmarken der gotischen Geschichte, wie die Bibelübersetzung Ulfilas, die Eroberung und Plünderung Roms 410 n. Chr. oder die demonstrative Aufgabe der religiösen Differenz durch König Rekkared, werden erst durch diesen neuen, umfassenden Kontext verständlich.
This reference paper describes the sampling and contents of the IZA Evaluation Dataset Survey and outlines its vast potential for research in labor economics. The data have been part of a unique IZA project to connect administrative data from the German Federal Employment Agency with innovative survey data to study the out-mobility of individuals to work. This study makes the survey available to the research community as a Scientific Use File by explaining the development, structure, and access to the data. Furthermore, it also summarizes previous findings with the survey data.
Biosensors for the detection of benzaldehyde and g-aminobutyric acid (GABA) are reported using aldehyde oxidoreductase PaoABC from Escherichia coli immobilized in a polymer containing bound low potential osmium redox complexes. The electrically connected enzyme already electrooxidizes benzaldehyde at potentials below −0.15 V (vs. Ag|AgCl, 1 M KCl). The pH-dependence of benzaldehyde oxidation can be strongly influenced by the ionic strength. The effect is similar with the soluble osmium redox complex and therefore indicates a clear electrostatic effect on the bioelectrocatalytic efficiency of PaoABC in the osmium containing redox polymer. At lower ionic strength, the pH-optimum is high and can be switched to low pH-values at high ionic strength. This offers biosensing at high and low pH-values. A “reagentless” biosensor has been formed with enzyme wired onto a screen-printed electrode in a flow cell device. The response time to addition of benzaldehyde is 30 s, and the measuring range is between 10–150 µM and the detection limit of 5 µM (signal to noise ratio 3:1) of benzaldehyde. The relative standard deviation in a series (n = 13) for 200 µM benzaldehyde is 1.9%. For the biosensor, a response to succinic semialdehyde was also identified. Based on this response and the ability to work at high pH a biosensor for GABA is proposed by coimmobilizing GABA-aminotransferase (GABA-T) and PaoABC in the osmium containing redox polymer.
Purpose: Mirror therapy can improve motor and sensory functions, but effects of the mirror illusion on primary motor and somatosensory cortex could not be established consistently.
Methods: Fifteen right handed healthy volunteers performed or observed a finger-thumb opposition task. Cerebral activations during normal movement (NOR), mirrored movement (MIR) and movement observation (OBS) by means of a video chain were recorded with functional magnetic resonance imaging (fMRI). Activation sizes in movement > static conditions were identified using SPM8 (p < 0.001, unc.) and attributed to predefined areas employing the Anatomy toolbox 1.8. Laterality indices for the responsive areas were calculated on the basis of the number of activated voxels.
Results: Relevant bilateral BOLD responses were found in primary motor (M1) and somatosensory (S1 - BA 2, 3b and 3a) cortex, premotor and parietal areas and V5. When comparing MIR to NOR, no significant change of contralateral activation in M1 was found, but clearly at S1 with differences between hands.
Conclusion: The mirror illusion does not elicit immediate changes in motor areas, yet there is a direct effect on somatosensory areas, especially for left hand movements. These results suggest different effects of mirror therapy on processing and rehabilitation of motor and sensory function.
This essay approaches T. S. Eliot's Four Quartets (1935-1942) from the perspectives of Eve Kosofsky Sedgwick's critical practice of reparative reading and of Paul Ricoeur's poststructuralist hermeneutics. It demonstrates that Sedgwick's and Ricoeur's approaches can be productively combined to investigate hermeneutic processes in which the textual energy of a dissemination of meaning is redirected by a reparative or integrative impulse. In Four Quartets, this impetus induces the creation of semantic innovation through a violation of semantic pertinence, that is, through novel, tensional and provisional connections between formerly separate textual elements and semantic units.
Environmental change is likely to have a strong impact on biodiversity, and many species may shift their distribution in response. In this study, we aimed at projecting the availability of suitable habitat for an endangered amphibian species, the Fire-bellied toad Bombina bombina, in Brandenburg (north-eastern Germany). We modelled a potential habitat distribution map based on (1) a database with 10,581 presence records for Bombina from the years 1990 to 2009, (2) current estimates for ecogeographical variables (EGVs) and (3) the future projection of these EGVs according to the statistical regional model, respectively, the soil and water integrated model, applying the maximum entropy approach (Maxent). By comparing current and potential future distributions, we evaluated the projected change in distribution of suitable habitats and identified the environmental variables most associated with habitat suitability that turned out to be climatic variables related to the hydrological cycle. Under the applied scenario, our results indicate increasing habitat suitability in many areas and an extended range of suitable habitats. However, even if the environmental conditions in Brandenburg may change as predicted, it is questionable whether the Fire-bellied toad will truly benefit, as dispersal abilities of amphibian species are limited and strongly influenced by anthropogenic disturbances, that is, intensive agriculture, habitat destruction and fragmentation. Furthermore, agronomic pressure is likely to increase on productive areas with fertile soils and high water retention capacities, indeed those areas suitable for B. bombina. All these changes may affect temporary pond hydrology as well as the reproductive success and breeding phenology of toads.
Increasing attempts are made to understand the factors responsible for both the demographic and genetic depletion in amphibian populations. Landscape genetics aims at a spatially explicit correlation of genetic population parameters to landscape features. Using data from the endangered fire-bellied toad Bombina bombina in Brandenburg (Northeastern Germany), we performed an environmental niche factor analysis (ENFA), relating demographic (abundance) and genetic (diversity at 17 microsatellite loci and partial sequences of the mitochondrial control region in 434 individuals from 16 populations) parameters to ecological and anthropogenic variables such as temperature, precipitation, soil wetness, water runoff, vegetation density, and road/traffic impact. We found significant correlations between road disturbance and observed heterozygosity and between soil wetness and mitochondrial diversity. As the influences of the environmental variables can differ between different indicators for genetic diversity, population size and abundance data, our ENFA-based landscape genetics approach allows us to put various aspects of long- versus short term effective population size and genetic connectivity into an ecological and spatially explicit context, enabling potentially even forecast assessment under future environmental scenarios.
Time-Travel-Treasures
(2014)
We isolated and characterized 16 new di- and tetranudeotide microsatellite markers for the critically endangered Asian box turtle genus Cuora, focusing on the "Cuora trifasciata" species complex. The new markers were then used to analyse genetic variability and divergence amongst five described species within this complex, namely C. aurocapitata (n = 18), C. cyclornata (n = 31), C. pani (n = 6), C. trifasciata (n = 58), and C. zhoui (n = 7). Our results support the view that all five species represent valid taxa. Within two species (C. trifasciata and C. cyclornata), two distinct morphotypes were corroborated by microsatellite divergence. For three individuals, morphologically identified as being of hybrid origin, the hybrid status was confirmed by our genetic analysis. Our results confirm the controversial species (Cuora aurocapitata, C. cyclornata) and subspecies/morphotypes (C. cyclornata meieri, C. trifasciata cf. trifasciata) to be genetically distinct, which has critical implications for conservation strategies.
Unstetige Galerkin-Diskretisierung niedriger Ordnung in einem atmosphärischen Multiskalenmodell
(2014)
Die Dynamik der Atmosphäre der Erde umfasst einen Bereich von mikrophysikalischer Turbulenz über konvektive Prozesse und Wolkenbildung bis zu planetaren Wellenmustern. Für Wettervorhersage und zur Betrachtung des Klimas über Jahrzehnte und Jahrhunderte ist diese Gegenstand der Modellierung mit numerischen Verfahren. Mit voranschreitender Entwicklung der Rechentechnik sind Neuentwicklungen der dynamischen Kerne von Klimamodellen, die mit der feiner werdenden Auflösung auch entsprechende Prozesse auflösen können, notwendig. Der dynamische Kern eines Modells besteht in der Umsetzung (Diskretisierung) der grundlegenden dynamischen Gleichungen für die Entwicklung von Masse, Energie und Impuls, so dass sie mit Computern numerisch gelöst werden können. Die vorliegende Arbeit untersucht die Eignung eines unstetigen Galerkin-Verfahrens niedriger Ordnung für atmosphärische Anwendungen. Diese Eignung für Gleichungen mit Wirkungen von externen Kräften wie Erdanziehungskraft und Corioliskraft ist aus der Theorie nicht selbstverständlich. Es werden nötige Anpassungen beschrieben, die das Verfahren stabilisieren, ohne sogenannte „slope limiter” einzusetzen. Für das unmodifizierte Verfahren wird belegt, dass es nicht geeignet ist, atmosphärische Gleichgewichte stabil darzustellen. Das entwickelte stabilisierte Modell reproduziert eine Reihe von Standard-Testfällen der atmosphärischen Dynamik mit Euler- und Flachwassergleichungen in einem weiten Bereich von räumlichen und zeitlichen Skalen. Die Lösung der thermischen Windgleichung entlang der mit den Isobaren identischen charakteristischen Kurven liefert atmosphärische Gleichgewichtszustände mit durch vorgegebenem Grundstrom einstellbarer Neigung zu(barotropen und baroklinen)Instabilitäten, die für die Entwicklung von Zyklonen wesentlich sind. Im Gegensatz zu früheren Arbeiten sind diese Zustände direkt im z-System(Höhe in Metern)definiert und müssen nicht aus Druckkoordinaten übertragen werden.Mit diesen Zuständen, sowohl als Referenzzustand, von dem lediglich die Abweichungen numerisch betrachtet werden, und insbesondere auch als Startzustand, der einer kleinen Störung unterliegt, werden verschiedene Studien der Simulation von barotroper und barokliner Instabilität durchgeführt. Hervorzuheben ist dabei die durch die Formulierung von Grundströmen mit einstellbarer Baroklinität ermöglichte simulationsgestützte Studie des Grades der baroklinen Instabilität verschiedener Wellenlängen in Abhängigkeit von statischer Stabilität und vertikalem Windgradient als Entsprechung zu Stabilitätskarten aus theoretischen Betrachtungen in der Literatur.
Das Europäische Parlament ist zweifelsohne die mächtigste parlamentarische Versammlung auf supranationaler Ebene. Das provoziert die Frage, wie Entscheidungen in diesem Parlament gefällt werden und wie sie begründet werden können. Darin liegt das Hauptanliegen dieser Arbeit, die zur Beantwortung dieser Frage auf soziologische Ansätze der Erklärung sozialen Handelns zurückgreift und damit einen neuen Zugang zur Beobachtung parlamentarischen Handelns schafft. Dabei arbeitet sie heraus, wie wichtig es ist, bei der Analyse politischer Entscheidungsprozesse zu beachten, wie politische Probleme von Akteuren interpretiert und gegenüber Verhandlungspartnern dargestellt werden. An den Fallbeispielen der Entscheidungsprozesse zur Dienstleistungsrichtlinie, zur Chemikalien-Verordnung REACH und dem TDIP (CIA)-Ausschuss in der Legislaturperiode 2004–2009, wird der soziale Mechanismus dargestellt, der hinter Einigungen im Europäischen Parlament steckt. Kultur als Interpretation der Welt wird so zum Schlüssel des Verständnisses politischer Entscheidungen auf supranationaler Ebene.
Formation of a Eu(III) borate solid species from a weak Eu(III) borate complex in aqueous solution
(2014)
In the presence of polyborates (detected by 11B-NMR) the formation of a weak Eu(III) borate complex (lg β11 ∼ 2, estimated) was observed by time-resolved laser-induced fluorescence spectroscopy (TRLFS). This complex is a precursor for the formation of a solid Eu(III) borate species. The formation of this solid in solution was investigated by TRLFS as a function of the total boron concentration: the lower the total boron concentration, the slower is the solid formation. The solid Eu(III) borate was characterized by IR spectroscopy, powder XRD and solid-state TRLFS. The determination of the europium to boron ratio portends the existence of pentaborate units in the amorphous solid.
Photoinduced excitation energy transfer and accompanying charge separation are elucidated for a supramolecular system of a single fullerene covalently linked to six pyropheophorbide-a dye molecules. Molecular dynamics simulations are performed to gain an atomistic picture of the architecture and the surrounding solvent. Excitation energy transfer among the dye molecules and electron transfer from the excited dyes to the fullerene are described by a mixed quantum–classical version of the Förster rate and the semiclassical Marcus rate, respectively. The mean characteristic time of energy redistribution lies in the range of 10 ps, while electron transfer proceeds within 150 ps. In between, on a 20 to 50 ps time-scale, conformational changes take place in the system. This temporal hierarchy of processes guarantees efficient charge separation, if the structure is exposed to a solvent. The fast energy transfer can adopt the dye excitation to the actual conformation. In this sense, the probability to achieve charge separation is large enough since any dominance of unfavorable conformations that exhibit a large dye–fullerene distance is circumvented. And the slow electron transfer may realize an averaging with respect to different conformations. To confirm the reliability of our computations, ensemble measurements on the charge separation dynamics are simulated and a very good agreement with the experimental data is obtained.
The synthesis of two novel types of π-expanded coumarins has been developed. Modified Knoevenagel bis-condensation afforded 3,9-dioxa-perylene-2,8-diones. Subsequent oxidative aromatic coupling or light driven electrocyclization reaction led to dibenzo-1,7-dioxacoronene-2,8-dione. Unparalleled synthetic simplicity, straightforward purification and superb optical properties have the potential to bring these perylene and coronene analogs towards various applications.
Two-photon polymerization of hydrogels – versatile solutions to fabricate well-defined 3D structures
(2014)
Hydrogels are cross-linked water-containing polymer networks that are formed by physical, ionic or covalent interactions. In recent years, they have attracted significant attention because of their unique physical properties, which make them promising materials for numerous applications in food and cosmetic processing, as well as in drug delivery and tissue engineering. Hydrogels are highly water-swellable materials, which can considerably increase in volume without losing cohesion, are biocompatible and possess excellent tissue-like physical properties, which can mimic in vivo conditions. When combined with highly precise manufacturing technologies, such as two-photon polymerization (2PP), well-defined three-dimensional structures can be obtained. These structures can become scaffolds for selective cell-entrapping, cell/drug delivery, sensing and prosthetic implants in regenerative medicine. 2PP has been distinguished from other rapid prototyping methods because it is a non-invasive and efficient approach for hydrogel cross-linking. This review discusses the 2PP-based fabrication of 3D hydrogel structures and their potential applications in biotechnology. A brief overview regarding the 2PP methodology and hydrogel properties relevant to biomedical applications is given together with a review of the most important recent achievements in the field.
Werner Mittenzwei’s article of 1967, the title of which coined the term “Brecht-Lukács-Debatte”, is widely considered as a milestone in the development of East German literary criticism towards an “emancipation” from party politics. By placing Mittenzwei’s contribution in the wider context of discussions about the literature of the GDR, within the SED and the writers’ union as well as at international conferences, this article attempts to trace the emergence of “Umfunktionierung” both as a key term and in its official approval by the party.
Il ciclo dei trentasei Contorni danteschi del pittore e disegnatore berlinese Giovanni Bonaventura Genelli (1798-1868) rappresenta un interessante tentativo d’interpretare il testo della Commedia alla luce dei principi del classicismo tedesco, sull’esempio di Carstens e di Koch e, in parte di Flaxman da cui però Genelli si distingue per continua ricerca volta ad esprimere la plasticità delle forme. Caratteristica precipua delle sue illustrazioni è inoltre il ricorso continuo sia alla scultura antica che agli affreschi michelangioleschi della Sistina come repertorio iconografico. L’articolo approfondisce questi aspetti con particolare riferimento alle sedici tavole dedicate all’Inferno.
Otto Braun
(2014)
Otto Braun war von 1921 bis 1932 mit kurzen Unterbrechungen Ministerpräsident des Freistaates Preußen. Er war sowohl überzeugter sozialer Demokrat als auch Preuße und betrieb eine entschlossene Reformpolitik, die zwar umstritten war, sich aber stets im Rahmen der Legalität bewegte. Die Grenzen dieses Ansatzes wurden am Ende der Weimarer Republik deutlich, als seine Regierung mit dem sogenannten »Preußenschlag« vom 20. Juli 1932 entmachtet wurde und Braun in Verkennung der neuen machtpolitischen Realitäten vergeblich versuchte, mit legalen Maßnahmen dem illegalen Vorgehen der Reichsregierung entgegenzutreten.
A new functional luminescent lanthanide complex (LLC) has been synthesized with terbium as a central lanthanide ion and biotin as a functional moiety. Unlike in typical lanthanide complexes assembled via carboxylic moieties, in the presented complex, four phosphate groups are chelating the central lanthanide ion. This special chemical assembly enhances the complex stability in phosphate buffers conventionally used in biochemistry. The complex synthesis strategy and photophysical properties are described as well as the performance in time-resolved Förster Resonance Energy Transfer (FRET) assays. In those assays, this biotin-LLC transferred energy either to acceptor organic dyes (Cy5 or AF680) labelled on streptavidin or to quantum dots (QD655 or QD705) surface-functionalised with streptavidins. The permanent spatial donor–acceptor proximity is assured through strong and stable biotin–streptavidin binding. The energy transfer is evidenced from the quenching observed in donor emission and from a decrease in donor luminescence decay, both associated with simultaneous increase in acceptor intensity and in the decay time. The dye-based assays are realised in TRIS and in PBS, whereas QD-based systems are studied in borate buffer. The delayed emission analysis allows for quantifying the recognition process and for auto-fluorescence-free detection, which is particularly relevant for application in bioanalysis. In accordance with Förster theory, Förster-radii (R0) were found to be around 60 Å for organic dyes and around 105 Å for QDs. The FRET efficiency (η) reached 80% and 25% for dye and QD acceptors, respectively. Physical donor–acceptor distances (r) have been determined in the range 45–60 Å for organic dye acceptors, while for acceptor QDs between 120 Å and 145 Å. This newly synthesised biotin-LLC extends the class of highly sensitive analytical tools to be applied in the bioanalytical methods such as time-resolved fluoroimmunoassays (TR-FIA), luminescent imaging and biosensing.
This book presents an agile and model-driven approach to manage scientific workflows. The approach is based on the Extreme Model Driven Design (XMDD) paradigm and aims at simplifying and automating the complex data analysis processes carried out by scientists in their day-to-day work. Besides documenting the impact the workflow modeling might have on the work of natural scientists, this book serves three major purposes: 1. It acts as a primer for practitioners who are interested to learn how to think in terms of services and workflows when facing domain-specific scientific processes. 2. It provides interesting material for readers already familiar with this kind of tools, because it introduces systematically both the technologies used in each case study and the basic concepts behind them. 3. As the addressed thematic field becomes increasingly relevant for lectures in both computer science and experimental sciences, it also provides helpful material for teachers that plan similar courses.
Potentiality of nanosized materials has been largely proved but a closer look shows that a significant percentage of this research is related to oxides and metals, while the number drastically drops for metallic ceramics, namely transition metal nitrides and metal carbides. The lack of related publications do not reflect their potential but rather the difficulties related to their synthesis as dense and defect-free structures, fundamental prerequisites for advanced mechanical applications.
The present habilitation work aims to close the gap between preparation and processing, indicating novel synthetic pathways for a simpler and sustainable synthesis of transition metal nitride (MN) and carbide (MC) based nanostructures and easier processing thereafter. In spite of simplicity and reliability, the designed synthetic processes allow the production of functional materials, with the demanded size and morphology.
The goal was achieved exploiting classical and less-classical precursors, ranging from common metal salts and molecules (e.g. urea, gelatin, agar, etc), to more exotic materials, such as leafs, filter paper and even wood. It was found that the choice of precursors and reaction conditions makes it possible to control chemical composition (going for instance from metal oxides to metal oxy-nitrides to metal nitrides, or from metal nitrides to metal carbides, up to quaternary systems), size (from 5 to 50 nm) and morphology (going from mere spherical nanoparticles to rod-like shapes, fibers, layers, meso-porous and hierarchical structures, etc). The nature of the mixed precursors also allows the preparation of metal nitrides/carbides based nanocomposites, thus leading to multifunctional materials (e.g. MN/MC@C, MN/MC@PILs, etc) but also allowing dispersion in liquid media. Control over composition, size and morphology is obtained with simple adjustment of the main route, but also coupling it with processes such as electrospin, aerosol spray, bio-templating, etc. Last but not least, the nature of the precursor materials also allows easy processing, including printing, coating, casting, film and thin layers preparation, etc).
The designed routes are, concept-wise, similar and they all start by building up a secondary metal ion-N/C precursor network, which converts, upon heat treatment, into an intermediate “glass”. This glass stabilizes the nascent nanoparticles during their nucleation and impairs their uncontrolled growth during the heat treatment (scheme 1). This way, one of the main problems related to the synthesis of MN/MC, i.e. the need of very high temperature, could also be overcome (from up to 2000°C, for classical synthesis, down to 700°C in the present cases). The designed synthetic pathways are also conceived to allow usage of non-toxic compounds and to minimize (or even avoid) post-synthesis purification, still bringing to phase pure and well-defined (crystalline) nanoparticles.
This research aids to simplify the preparation of MN/MC, making these systems now readily available in suitable amounts both for fundamental and applied science. The prepared systems have been tested (in some cases for the first time) in many different fields, e.g. battery (MnN0.43@C shown a capacity stabilized at a value of 230 mAh/g, with coulombic efficiencies close to 100%), as alternative magnetic materials (Fe3C nanoparticles were prepared with different size and therefore different magnetic behavior, superparamagnetic or ferromagnetic, showing a saturation magnetization value up to 130 emu/g, i.e. similar to the value expected for the bulk material), as filters and for the degradation of organic dyes (outmatching the performance of carbon), as catalysts (both as active phase but also as active support, leading to high turnover rate and, more interesting, to tunable selectivity). Furthermore, with this route, it was possible to prepare for the first time, to the best of our knowledge, well-defined and crystalline MnN0.43, Fe3C and Zn1.7GeN1.8O nanoparticles via bottom-up approaches.
Once the synthesis of these materials can be made straightforward, any further modification, combination, manipulation, is in principle possible and new systems can be purposely conceived (e.g. hybrids, nanocomposites, ferrofluids, etc).
The atmosphere over the Arctic Ocean is strongly influenced by the distribution of sea ice and open water. Leads in the sea ice produce strong convective fluxes of sensible and latent heat and release aerosol particles into the atmosphere. They increase the occurrence of clouds and modify the structure and characteristics of the atmospheric boundary layer (ABL) and thereby influence the Arctic climate.
In the course of this study aircraft measurements were performed over the western Arctic Ocean as part of the campaign PAMARCMIP 2012 of the Alfred Wegener Institute for Polar and Marine Research (AWI). Backscatter from aerosols and clouds within the lower troposphere and the ABL were measured with the nadir pointing Airborne Mobile Aerosol Lidar (AMALi) and dropsondes were launched to obtain profiles of meteorological variables. Furthermore, in situ measurements of aerosol properties, meteorological variables and turbulence were part of the campaign. The measurements covered a broad range of atmospheric and sea ice conditions.
In this thesis, properties of the ABL over Arctic sea ice with a focus on the influence of open leads are studied based on the data from the PAMARCMIP campaign. The height of the ABL is determined by different methods that are applied to dropsonde and AMALi backscatter profiles. ABL heights are compared for different flights representing different conditions of the atmosphere and of sea ice and open water influence. The different criteria for ABL height that are applied show large variation in terms of agreement among each other, depending on the characteristics of the ABL and its history. It is shown that ABL height determination from lidar backscatter by methods commonly used under mid-latitude conditions is applicable to the Arctic ABL only under certain conditions. Aerosol or clouds within the ABL are needed as a tracer for ABL height detection from backscatter. Hence an aerosol source close to the surface is necessary, that is typically found under the present influence of open water and therefore convective conditions. However it is not always possible to distinguish residual layers from the actual ABL. Stable boundary layers are generally difficult to detect.
To illustrate the complexity of the Arctic ABL and processes therein, four case studies are analyzed each of which represents a snapshot of the interplay between atmosphere and underlying sea ice or water surface. Influences of leads and open water on the aerosol and clouds within the ABL are identified and discussed. Leads are observed to cause the formation of fog and cloud layers within the ABL by humidity emission. Furthermore they decrease the stability and increase the height of the ABL and consequently facilitate entrainment of air and aerosol layers from the free troposphere.
Cyanobacteria produce about 40 percent of the world’s primary biomass, but also a variety of often toxic peptides such as microcystin. Mass developments, so called blooms, can pose a real threat to the drinking water supply in many parts of the world. This study aimed at characterizing the biological function of microcystin production in one of the most common bloom-forming cyanobacterium Microcystis aeruginosa.
In a first attempt, the effect of elevated light intensity on microcystin production and its binding to cellular proteins was studied. Therefore, conventional microcystin quantification techniques were combined with protein-biochemical methods. RubisCO, the key enzyme for primary carbon fixation was a major microcystin interaction partner. High light exposition strongly stimulated microcystin-protein interactions. Up to 60 percent of the total cellular microcystin was detected bound to proteins, i.e. inaccessible for standard quantification procedures. Underestimation of total microcystin contents when neglecting the protein fraction was also demonstrated in field samples. Finally, an immuno-fluorescence based method was developed to identify microcystin producing cyanobacteria in mixed populations.
The high light induced microcystin interaction with proteins suggested an impact of the secondary metabolite on the primary metabolism of Microcystis by e.g. modulating the activity of enzymes. For addressing that question, a comprehensive GC/MS-based approach was conducted to compare the accumulation of metabolites in the wild-type of Microcystis aeruginosa PCC 7806 and the microcystin deficient ΔmcyB mutant. From all 501 detected non-redundant metabolites 85 (17 percent) accumulated significantly different in either of both genotypes upon high light exposition. Accumulation of compatible solutes in the ΔmcyB mutant suggests a role of microcystin in fine-tuning the metabolic flow to prevent stress related to excess light, high oxygen concentration and carbon limitation.
Co-analysis of the widely used model cyanobacterium Synechocystis PCC 6803 revealed profound metabolic differences between species of cyanobacteria. Whereas Microcystis channeled more resources towards carbohydrate synthesis, Synechocystis invested more in amino acids. These findings were supported by electron microscopy of high light treated cells and the quantification of storage compounds. While Microcystis accumulated mainly glycogen to about 8.5 percent of its fresh weight within three hours, Synechocystis produced higher amounts of cyanophycin. The results showed that the characterization of species-specific metabolic features should gain more attention with regard to the biotechnological use of cyanobacteria.
Modern microscopic techniques following the stochastic motion of labelled tracer particles have uncovered significant deviations from the laws of Brownian motion in a variety of animate and inanimate systems. Such anomalous diffusion can have different physical origins, which can be identified from careful data analysis. In particular, single particle tracking provides the entire trajectory of the traced particle, which allows one to evaluate different observables to quantify the dynamics of the system under observation. We here provide an extensive overview over different popular anomalous diffusion models and their properties. We pay special attention to their ergodic properties, highlighting the fact that in several of these models the long time averaged mean squared displacement shows a distinct disparity to the regular, ensemble averaged mean squared displacement. In these cases, data obtained from time averages cannot be interpreted by the standard theoretical results for the ensemble averages. Here we therefore provide a comparison of the main properties of the time averaged mean squared displacement and its statistical behaviour in terms of the scatter of the amplitudes between the time averages obtained from different trajectories. We especially demonstrate how anomalous dynamics may be identified for systems, which, on first sight, appear to be Brownian. Moreover, we discuss the ergodicity breaking parameters for the different anomalous stochastic processes and showcase the physical origins for the various behaviours. This Perspective is intended as a guidebook for both experimentalists and theorists working on systems, which exhibit anomalous diffusion.
Modern microscopic techniques following the stochastic motion of labelled tracer particles have uncovered significant deviations from the laws of Brownian motion in a variety of animate and inanimate systems. Such anomalous diffusion can have different physical origins, which can be identified from careful data analysis. In particular, single particle tracking provides the entire trajectory of the traced particle, which allows one to evaluate different observables to quantify the dynamics of the system under observation. We here provide an extensive overview over different popular anomalous diffusion models and their properties. We pay special attention to their ergodic properties, highlighting the fact that in several of these models the long time averaged mean squared displacement shows a distinct disparity to the regular, ensemble averaged mean squared displacement. In these cases, data obtained from time averages cannot be interpreted by the standard theoretical results for the ensemble averages. Here we therefore provide a comparison of the main properties of the time averaged mean squared displacement and its statistical behaviour in terms of the scatter of the amplitudes between the time averages obtained from different trajectories. We especially demonstrate how anomalous dynamics may be identified for systems, which, on first sight, appear to be Brownian. Moreover, we discuss the ergodicity breaking parameters for the different anomalous stochastic processes and showcase the physical origins for the various behaviours. This Perspective is intended as a guidebook for both experimentalists and theorists working on systems, which exhibit anomalous diffusion.
New porous materials based on covalently connected monomers are presented. The key step of the synthesis is an acetalisation reaction. In previous years we used acetalisation reactions extensively to build up various molecular rods. Based on this approach, investigations towards porous polymeric materials were conducted by us. Here we wish to present the results of these studies in the synthesis of 1D polyacetals and porous 3D polyacetals. By scrambling experiments with 1D acetals we could prove that exchange reactions occur between different building blocks (evidenced by MALDI-TOF mass spectrometry). Based on these results we synthesized porous 3D polyacetals under the same mild conditions.
New porous materials based on covalently connected monomers are presented. The key step of the synthesis is an acetalisation reaction. In previous years we used acetalisation reactions extensively to build up various molecular rods. Based on this approach, investigations towards porous polymeric materials were conducted by us. Here we wish to present the results of these studies in the synthesis of 1D polyacetals and porous 3D polyacetals. By scrambling experiments with 1D acetals we could prove that exchange reactions occur between different building blocks (evidenced by MALDI-TOF mass spectrometry). Based on these results we synthesized porous 3D polyacetals under the same mild conditions.
Picosecond X-ray absorption spectroscopy (XAS) is used to investigate the electronic and structural dynamics initiated by plasmon excitation of 1.8 nm diameter Au nanoparticles (NPs) functionalised with 1-hexanethiol. We show that 100 ps after photoexcitation the transient XAS spectrum is consistent with an 8% expansion of the Au–Au bond length and a large increase in disorder associated with melting of the NPs. Recovery of the ground state occurs with a time constant of ∼1.8 ns, arising from thermalisation with the environment. Simulations reveal that the transient spectrum exhibits no signature of charge separation at 100 ps and allows us to estimate an upper limit for the quantum yield (QY) of this process to be <0.1.
Picosecond X-ray absorption spectroscopy (XAS) is used to investigate the electronic and structural dynamics initiated by plasmon excitation of 1.8 nm diameter Au nanoparticles (NPs) functionalised with 1-hexanethiol. We show that 100 ps after photoexcitation the transient XAS spectrum is consistent with an 8% expansion of the Au–Au bond length and a large increase in disorder associated with melting of the NPs. Recovery of the ground state occurs with a time constant of ∼1.8 ns, arising from thermalisation with the environment. Simulations reveal that the transient spectrum exhibits no signature of charge separation at 100 ps and allows us to estimate an upper limit for the quantum yield (QY) of this process to be <0.1.
We study the thermal Markovian diffusion of tracer particles in a 2D medium with spatially varying diffusivity D(r), mimicking recently measured, heterogeneous maps of the apparent diffusion coefficient in biological cells. For this heterogeneous diffusion process (HDP) we analyse the mean squared displacement (MSD) of the tracer particles, the time averaged MSD, the spatial probability density function, and the first passage time dynamics from the cell boundary to the nucleus. Moreover we examine the non-ergodic properties of this process which are important for the correct physical interpretation of time averages of observables obtained from single particle tracking experiments. From extensive computer simulations of the 2D stochastic Langevin equation we present an in-depth study of this HDP. In particular, we find that the MSDs along the radial and azimuthal directions in a circular domain obey anomalous and Brownian scaling, respectively. We demonstrate that the time averaged MSD stays linear as a function of the lag time and the system thus reveals a weak ergodicity breaking. Our results will enable one to rationalise the diffusive motion of larger tracer particles such as viruses or submicron beads in biological cells.
We study the thermal Markovian diffusion of tracer particles in a 2D medium with spatially varying diffusivity D(r), mimicking recently measured, heterogeneous maps of the apparent diffusion coefficient in biological cells. For this heterogeneous diffusion process (HDP) we analyse the mean squared displacement (MSD) of the tracer particles, the time averaged MSD, the spatial probability density function, and the first passage time dynamics from the cell boundary to the nucleus. Moreover we examine the non-ergodic properties of this process which are important for the correct physical interpretation of time averages of observables obtained from single particle tracking experiments. From extensive computer simulations of the 2D stochastic Langevin equation we present an in-depth study of this HDP. In particular, we find that the MSDs along the radial and azimuthal directions in a circular domain obey anomalous and Brownian scaling, respectively. We demonstrate that the time averaged MSD stays linear as a function of the lag time and the system thus reveals a weak ergodicity breaking. Our results will enable one to rationalise the diffusive motion of larger tracer particles such as viruses or submicron beads in biological cells.