An evaluation of the distributions of polychlorinated biphenyls and organic matter in coastal sediments

The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems. Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory < 1% are in sediments near population centres while ≥ 90% is in remote areas (> 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.

Overlapping of ESP/EAP and content courses revisited

[ES] This paper deals with some key issues in a controversial topic, that of the existing overlapping between ESP/EAP courses and simultaneously-run content courses. Some examples are provided and analyzed to be aware of the need of ESP/EAP practitioners to have a fairly deep knowledge of those technical matters they have to deal with in order to be as genuinely communicative as possible. Later on, a list of principles for designing successful ESP/EAP courses is presented and justified. After putting into practice a communicative approach founded on those principles for a period of five years, the opinion of those students who have taken two ESP/EAP courses was gathered –an ad hoc questionnaire was developed for the purpose–. data are analyzed to hypothesize the long-run correlation between applying the above mentioned principles and the positive opinion of students on their teachers when those principles are applied at university level.

Face and eye detection on hard datasets

[EN] This paper analyzes the detection and localization performance of the participating face and eye algorithms compared with the Viola Jones detector and four leading commercial face detectors. Performance is characterized under the different conditions and parameterized by per-image brightness and contrast. In localization accuracy for eyes, the groups/companies focusing on long-range face detection outperform leading commercial applications.

Non-Markovian stochastic processes and their applications: from anomalous diffusion to time series analysis

This work provides a forward step in the study and comprehension of the relationships between stochastic processes and a certain class of integral-partial differential equation, which can be used in order to model anomalous diffusion and transport in statistical physics. In the first part, we brought the reader through the fundamental notions of probability and stochastic processes, stochastic integration and stochastic differential equations as well. In particular, within the study of H-sssi processes, we focused on fractional Brownian motion (fBm) and its discrete-time increment process, the fractional Gaussian noise (fGn), which provide examples of non-Markovian Gaussian processes. The fGn, together with stationary FARIMA processes, is widely used in the modeling and estimation of long-memory, or long-range dependence (LRD). Time series manifesting long-range dependence, are often observed in nature especially in physics, meteorology, climatology, but also in hydrology, geophysics, economy and many others. We deepely studied LRD, giving many real data examples, providing statistical analysis and introducing parametric methods of estimation. Then, we introduced the theory of fractional integrals and derivatives, which indeed turns out to be very appropriate for studying and modeling systems with long-memory properties. After having introduced the basics concepts, we provided many examples and applications. For instance, we investigated the relaxation equation with distributed order time-fractional derivatives, which describes models characterized by a strong memory component and can be used to model relaxation in complex systems, which deviates from the classical exponential Debye pattern. Then, we focused in the study of generalizations of the standard diffusion equation, by passing through the preliminary study of the fractional forward drift equation. Such generalizations have been obtained by using fractional integrals and derivatives of distributed orders. In order to find a connection between the anomalous diffusion described by these equations and the long-range dependence, we introduced and studied the generalized grey Brownian motion (ggBm), which is actually a parametric class of H-sssi processes, which have indeed marginal probability density function evolving in time according to a partial integro-differential equation of fractional type. The ggBm is of course Non-Markovian. All around the work, we have remarked many times that, starting from a master equation of a probability density function f(x,t), it is always possible to define an equivalence class of stochastic processes with the same marginal density function f(x,t). All these processes provide suitable stochastic models for the starting equation. Studying the ggBm, we just focused on a subclass made up of processes with stationary increments. The ggBm has been defined canonically in the so called grey noise space. However, we have been able to provide a characterization notwithstanding the underline probability space. We also pointed out that that the generalized grey Brownian motion is a direct generalization of a Gaussian process and in particular it generalizes Brownain motion and fractional Brownain motion as well. Finally, we introduced and analyzed a more general class of diffusion type equations related to certain non-Markovian stochastic processes. We started from the forward drift equation, which have been made non-local in time by the introduction of a suitable chosen memory kernel K(t). The resulting non-Markovian equation has been interpreted in a natural way as the evolution equation of the marginal density function of a random time process l(t). We then consider the subordinated process Y(t)=X(l(t)) where X(t) is a Markovian diffusion. The corresponding time-evolution of the marginal density function of Y(t) is governed by a non-Markovian Fokker-Planck equation which involves the same memory kernel K(t). We developed several applications and derived the exact solutions. Moreover, we considered different stochastic models for the given equations, providing path simulations.

Sphärische Bürsten in polymeren Schmelzen

Colloidal nanoparticles are additives to improve or modify several properties of thermoplastic or elastic polymers. Usually colloid-polymer mixtures show phase separation due to the depletion effect. The strategy to overcome this depletion demixing was to prepare surface-modified colloidal particles, which can be blended with linear polymer chains homogeneous. A successful synthesis strategy for the preparation of hairy nanospheres was developed by grafting polystyrene macromonomer chains onto polyorganosiloxane microgels. The number of hairs per particle with a core radius of approximately 10nm exceeded 150 hairs in all cases. The molecular weight of the hairs variied between 4000-18000g/mol.The compatibility of these hairy spheres mixed with linear polymer chains was investigated by AFM, TEM and SAXS. Homogeneous mixtures were found if the molecular weight of the polymer hairs on the particle surface is at least as large as the molecular weight of the matrix chains. If the chains are much shorter than the hairs, the colloidal hair corona is strongly swollen by the matrix polymer, leading to a long-range soft interparticle repulsion ('wet brush'). If hairs and chains are comparable in length, the corona shows much less volume swelling, leading to a short-range repulsive potential similar to hard sphere systems ('dry brush'). Polymerketten und Kolloidpartikel entmischen aufgrund von Depletion-Wechselwirkungen. Diese entropisch bedingte Entmischung konnte durch das Ankoppeln von Polymerhaaren verschiedenen Molekulargewichts auf die Kugeloberflächen der Kolloide bis zu hohen Konzentrationen vermieden werden. Zur Darstellung sphärischer Bürsten und haariger Tracerpartikel wurde eine neue Synthesestrategie ausgearbeitet und erfolgreich umgesetzt.Das Kompatibilitätsverhalten dieser sphärischen Bürsten in der Schmelze von Polymerketten als Matrix wurde mittels Elektronenmikroskopie und Kleinwinkelröntgenstreuung untersucht. Die Mischungen setzten sich aus sphärischen Bürsten und Matrixketten mit unterschiedlichen Molekulargewichten zusammen.Es zeigte sich, daß die Mischbarkeit entschieden durch das Verhältnis von Haarlänge zu Länge der Matrixketten beeinflußt wird.Aus den Untersuchungen des Relaxationsverhaltens mittels Rheologie und SAXS ergibt sich, daß das Konzept der 'dry brush'- und 'wet brush'-Systeme auf diese Mischungen übertragbar ist. Die Volumenquellung der Haarcorona durch die Matrixketten ist, wie die Experimente gezeigt haben, bereits im Fall von Polymeren mit relativ niedrigen Molekulargewichten zu beobachten. Sie ist umso stärker ausgeprägt, je größer das Längenverhältnis zwischen Polymerhaaren und Matrixketten ist. Die Quellung bedeutet eine Vergrößerung des effektiven Radius der Partikel und entspricht somit einer Erhöhung des effektiven Volumenbruchs. Dies führt zur Ausbildung einer höheren Ordnung und zu einem Einfrieren der Relaxation dieser strukturellen Ordnung führt.

Untersuchung der Strukturdynamik arbeitender F1-ATPase und ATP-Synthase aus Micrococcus luteus in Einzelschußexperimenten mit Synchrotronstrahlung

ZusammenfassungDie ATP-Synthase koppelt im Energiestoffwechsel der Zellen den Protonentransport über die biologische Membran mit der Synthese des energiespeichernden Moleküls ATP aus ADP und Phosphat. ATP-Synthasen bestehen aus 2 Subkomplexen, wobei der katalytische F1-Teil von der membranständigen Domäne abgelöst werden kann und nur zur ATP-Hydrolyse fähig ist. Der hochkooperative Reaktionsmechanismus der dreizentrigen ATP-Synthasen ist weitgehend unklar.Im Rahmen dieser Arbeit wurde der ATP-Synthasekomplex und ihr wasserlösliches katalytisches F1-Fragment aus Micrococcus luteus in präparativem Maßstab mittels chromatographischer Trennmethoden isoliert. Die Überprüfung der Funktionalität beider Enzyme erfolgte mit enzymatischen Methoden. Durch zeitaufgelöste Röntgenkleinwinkelstreuung wurde die Strukturdynamik der arbeitenden ATP-Synthase und ihres F1-Fragmentes aus Micrococcus luteus im Laufe des ATP-Hydrolysezyklus untersucht. Diese Methode diente zum Nachweis weiträumiger Konformationsänderungen innerhalb der arbeitenden Enzyme unter nativen physiologischen Bedingungen. Die zeitaufgelösten Streuexperimente fanden an der ESRF (Europäische Synchrotronstrahlungsquelle) in Grenoble (F) statt. Dort wurden für beide Enzyme im Laufe des ATP-Hydrolysezykus molekulare Bewegungen nachgewiesen. Als Referenz zu den zeitaufgelösten Messungen dienten statische Messungen zur Strukturuntersuchung der Proteine am schwächeren DESY. Anhand dieser Strukturdaten wurden Molekülmodelle der F1-ATPase und ATP-Synthase aus Micrococcus luteus konstruiert. Das Molekülmodell der F1-ATPase war die Grundlage zur Modellierung einzelner Teilschritte des ATP-Hydrolysezyklus bei 20°C. Die experimentellen Daten wurden mit einer Kippbewegung der membranseitigen Domäne der katalytischen b-Untereinheiten der F1-ATPase während des ATP-Hydrolysezyklus interpretiert.

Investigations on formation and specification of neural precursor cells in the central nervous system of the Drosophila melanogaster embryo

Investigations on formation and specification of neural precursor cells in the central nervous system of the Drosophila melanogaster embryoSpecification of a unique cell fate during development of a multicellular organism often is a function of its position. The Drosophila central nervous system (CNS) provides an ideal system to dissect signalling events during development that lead to cell specific patterns. Different cell types in the CNS are formed from a relatively few precursor cells, the neuroblasts (NBs), which delaminate from the neurogenic region of the ectoderm. The delamination occurs in five waves, S1-S5, finally leading to a subepidermal layer consisting of about 30 NBs, each with a unique identity, arranged in a stereotyped spatial pattern in each hemisegment. This information depends on several factors such as the concentrations of various morphogens, cell-cell interactions and long range signals present at the position and time of its birth. The early NBs, delaminating during S1 and S2, form an orthogonal array of four rows (2/3,4,5,6/7) and three columns (medial, intermediate, and lateral) . However, the three column and four row-arrangement pattern is only transitory during early stages of neurogenesis which is obscured by late emerging (S3-S5) neuroblasts (Doe and Goodman, 1985; Goodman and Doe, 1993). Therefore the aim of my study has been to identify novel genes which play a role in the formation or specification of late delaminating NBs.In this study the gene anterior open or yan was picked up in a genetic screen to identity novel and yet unidentified genes in the process of late neuroblast formation and specification. I have shown that the gene yan is responsible for maintaining the cells of the neuroectoderm in an undifferentiated state by interfering with the Notch signalling mechanism. Secondly, I have studied the function and interactions of segment polarity genes within a certain neuroectodermal region, namely the engrailed (en) expressing domain, with regard to the fate specification of a set of late neuroblasts, namely NB 6-4 and NB 7-3. I have dissected the regulatory interaction of the segment polarity genes wingless (wg), hedgehog (hh) and engrailed (en) as they maintain each other’s expression to show that En is a prerequisite for neurogenesis and show that the interplay of the segmentation genes naked (nkd) and gooseberry (gsb), both of which are targets of wingless (wg) activity, leads to differential commitment of NB 7-3 and NB 6-4 cell fate. I have shown that in the absence of either nkd or gsb one NB fate is replaced by the other. However, the temporal sequence of delamination is maintained, suggesting that formation and specification of these two NBs are under independent control.

GC/MS-Meßsystem für Nicht-Methan-Kohlenwasserstoffe

Im Rahmen der Projekte CARIBIC ('Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container') und INDOEX ('Indian Ocean Experi-ment') wurde ein Gaschromatograph mit Massenspektrometer zur Analyse von Luftproben auf Nicht-Methan-Kohlenwasserstoffe (NMKW) im ppb- und ppt-Bereich entwickelt. Während INDOEX erfolgte die Probennahme auf dem Forschungsschiff Ronald Brown, während CARIBIC mit einem automatischen Probensammler an Bord eines Passagierflugzeuges (Boeing 767-ER, LTU). Die NMKW-Meßergebnisse wurden zusammen mit Ergebnissen von Mes-sungen von Kohlenmonoxid (CO, einschließlich Isotopenzusam-mensetzung), Ozon (O3), Methan (CH4), Kohlendioxid (CO2), Distickstoffmonoxid (N2O), Schwefelhexafluorid (SF6) und Aerosoleigenschaften sowie meteorologischen Daten inter-pretiert. Während INDOEX (Februar / März 1999) wurde in der maritimen Grenzschicht (MBL) des Indischen Ozeans (IO) eine starke Variabilität diverser Spurengase beobachtet, die teilweise durch regionale Emissionen hervorgerufen wurde, die stärkste Variabilität war jedoch durch Langstrecken-transport aus mittleren Breiten der Nordhemisphäre bedingt. Aufgrund der Abweichungen vom klimatologischen Mittel, sollten regionale Quellen die MBL des IO im allgemeinen stärker beeinflussen. Die Einteilung des IO in meteorologi-sche Luftmassenregime wurde bestätigt. Starke Spurengasgra-dienten an der innertropischen Konvergenzzone (ITCZ) zeigen, daß die ITCZ in erster Linie den Austausch von Luftmassen zwischen den Hemisphären behindert. Bei CARIBIC werden Messungen von Spurengasen (ein-(schließlich NMKW) und Aerosoleigenschaften auf Flügen in der oberen Troposphäre / unteren Stratosphäre durchgeführt. Während eines Flug über Afrika wurden der Einfluß von durch Konvektion in die obere Troposphäre eingebrachten, frischen Abgasen aus Biomassenverbrennung nachgewiesen. Andere Luft-massen wurden durch Emissionen von Erdgas bzw. durch die Stratosphäre beeinflußt.

Sistemi riconfigurabili a basso consumo per applicazioni di monitoraggio distribuito

The term Ambient Intelligence (AmI) refers to a vision on the future of the information society where smart, electronic environment are sensitive and responsive to the presence of people and their activities (Context awareness). In an ambient intelligence world, devices work in concert to support people in carrying out their everyday life activities, tasks and rituals in an easy, natural way using information and intelligence that is hidden in the network connecting these devices. This promotes the creation of pervasive environments improving the quality of life of the occupants and enhancing the human experience. AmI stems from the convergence of three key technologies: ubiquitous computing, ubiquitous communication and natural interfaces. Ambient intelligent systems are heterogeneous and require an excellent cooperation between several hardware/software technologies and disciplines, including signal processing, networking and protocols, embedded systems, information management, and distributed algorithms. Since a large amount of fixed and mobile sensors embedded is deployed into the environment, the Wireless Sensor Networks is one of the most relevant enabling technologies for AmI. WSN are complex systems made up of a number of sensor nodes which can be deployed in a target area to sense physical phenomena and communicate with other nodes and base stations. These simple devices typically embed a low power computational unit (microcontrollers, FPGAs etc.), a wireless communication unit, one or more sensors and a some form of energy supply (either batteries or energy scavenger modules). WNS promises of revolutionizing the interactions between the real physical worlds and human beings. Low-cost, low-computational power, low energy consumption and small size are characteristics that must be taken into consideration when designing and dealing with WSNs. To fully exploit the potential of distributed sensing approaches, a set of challengesmust be addressed. Sensor nodes are inherently resource-constrained systems with very low power consumption and small size requirements which enables than to reduce the interference on the physical phenomena sensed and to allow easy and low-cost deployment. They have limited processing speed,storage capacity and communication bandwidth that must be efficiently used to increase the degree of local ”understanding” of the observed phenomena. A particular case of sensor nodes are video sensors. This topic holds strong interest for a wide range of contexts such as military, security, robotics and most recently consumer applications. Vision sensors are extremely effective for medium to long-range sensing because vision provides rich information to human operators. However, image sensors generate a huge amount of data, whichmust be heavily processed before it is transmitted due to the scarce bandwidth capability of radio interfaces. In particular, in video-surveillance, it has been shown that source-side compression is mandatory due to limited bandwidth and delay constraints. Moreover, there is an ample opportunity for performing higher-level processing functions, such as object recognition that has the potential to drastically reduce the required bandwidth (e.g. by transmitting compressed images only when something ‘interesting‘ is detected). The energy cost of image processing must however be carefully minimized. Imaging could play and plays an important role in sensing devices for ambient intelligence. Computer vision can for instance be used for recognising persons and objects and recognising behaviour such as illness and rioting. Having a wireless camera as a camera mote opens the way for distributed scene analysis. More eyes see more than one and a camera system that can observe a scene from multiple directions would be able to overcome occlusion problems and could describe objects in their true 3D appearance. In real-time, these approaches are a recently opened field of research. In this thesis we pay attention to the realities of hardware/software technologies and the design needed to realize systems for distributed monitoring, attempting to propose solutions on open issues and filling the gap between AmI scenarios and hardware reality. The physical implementation of an individual wireless node is constrained by three important metrics which are outlined below. Despite that the design of the sensor network and its sensor nodes is strictly application dependent, a number of constraints should almost always be considered. Among them: • Small form factor to reduce nodes intrusiveness. • Low power consumption to reduce battery size and to extend nodes lifetime. • Low cost for a widespread diffusion. These limitations typically result in the adoption of low power, low cost devices such as low powermicrocontrollers with few kilobytes of RAMand tenth of kilobytes of program memory with whomonly simple data processing algorithms can be implemented. However the overall computational power of the WNS can be very large since the network presents a high degree of parallelism that can be exploited through the adoption of ad-hoc techniques. Furthermore through the fusion of information from the dense mesh of sensors even complex phenomena can be monitored. In this dissertation we present our results in building several AmI applications suitable for a WSN implementation. The work can be divided into two main areas:Low Power Video Sensor Node and Video Processing Alghoritm and Multimodal Surveillance . Low Power Video Sensor Nodes and Video Processing Alghoritms In comparison to scalar sensors, such as temperature, pressure, humidity, velocity, and acceleration sensors, vision sensors generate much higher bandwidth data due to the two-dimensional nature of their pixel array. We have tackled all the constraints listed above and have proposed solutions to overcome the current WSNlimits for Video sensor node. We have designed and developed wireless video sensor nodes focusing on the small size and the flexibility of reuse in different applications. The video nodes target a different design point: the portability (on-board power supply, wireless communication), a scanty power budget (500mW),while still providing a prominent level of intelligence, namely sophisticated classification algorithmand high level of reconfigurability. We developed two different video sensor node: The device architecture of the first one is based on a low-cost low-power FPGA+microcontroller system-on-chip. The second one is based on ARM9 processor. Both systems designed within the above mentioned power envelope could operate in a continuous fashion with Li-Polymer battery pack and solar panel. Novel low power low cost video sensor nodes which, in contrast to sensors that just watch the world, are capable of comprehending the perceived information in order to interpret it locally, are presented. Featuring such intelligence, these nodes would be able to cope with such tasks as recognition of unattended bags in airports, persons carrying potentially dangerous objects, etc.,which normally require a human operator. Vision algorithms for object detection, acquisition like human detection with Support Vector Machine (SVM) classification and abandoned/removed object detection are implemented, described and illustrated on real world data. Multimodal surveillance: In several setup the use of wired video cameras may not be possible. For this reason building an energy efficient wireless vision network for monitoring and surveillance is one of the major efforts in the sensor network community. Energy efficiency for wireless smart camera networks is one of the major efforts in distributed monitoring and surveillance community. For this reason, building an energy efficient wireless vision network for monitoring and surveillance is one of the major efforts in the sensor network community. The Pyroelectric Infra-Red (PIR) sensors have been used to extend the lifetime of a solar-powered video sensor node by providing an energy level dependent trigger to the video camera and the wireless module. Such approach has shown to be able to extend node lifetime and possibly result in continuous operation of the node.Being low-cost, passive (thus low-power) and presenting a limited form factor, PIR sensors are well suited for WSN applications. Moreover techniques to have aggressive power management policies are essential for achieving long-termoperating on standalone distributed cameras needed to improve the power consumption. We have used an adaptive controller like Model Predictive Control (MPC) to help the system to improve the performances outperforming naive power management policies.

Strukturen und Phasen des beta-Eukryptits sowie die Sammlung von Beugungsdaten mit axialen q-Scans

Der 'gestopfte Hochquarz' ß-Eukryptit (LiAlSiO4) ist bekannt für seine außergewöhnliche anisotrope Li-Ionenleitfähigkeit und die nahe Null liegende thermische Ausdehnung.Untersucht wurde die temperaturabhängige ß-Eukryptit-Phasenabfolge, insbesondere die modulierte Phase. Deren Satellitenreflexe sind gegenüber den normalen Reflexen erheblich verbreitert, überlappen miteinander sowie mit den dazwischen liegenden 'a-Reflexen' zu Tripletts. Für die Separation der Triplett-Intensitäten waren bisherige Standardverfahren zur Beugungsdatensammlung ungeeignet. Mit 'axialen q-Scans' wurde ein neuartiges Verfahren entwickelt. Intensitäten wurden mit dem neu-entwickelten least squares-Programm GKLS aus 2000 Profilen seriell und automatisch gewonnen und erfolgreich auf Standarddaten skaliert. Die Verwendung verbreiterter Reflexprofile erwies sich als zulässig.Die Verbreiterung wurde auf eine verminderte Fernordnung der Modulation von 11 bis 16 Perioden zurückgeführt (Analyse mit der Gitterfunktion), womit ein ungewöhnliches beugungswinkelabhängiges Verhalten der Reflexbreiten korrespondiert und mit typischen Antiphasendomänendurchmessern (andere Autoren) korreliert.Eine verminderte Si-/ Al-Ordnung wird als ursächlich für geringe Domänengrößen und Fernordnung angesehen, sowie für Eigenschaften wie z.B. a/c-Verhältnisse, Ausdehnungskoeffizienten, Ionenleitfähigkeit, Strukturtyp und Umwandlungstemperaturen. Änderungen des SiO2-Gehaltes, der Temperatur oder der Si- /Al-Ordnung zeitigen für einige Eigenschaften ähnliche Wirkungen.Die gemittelte Struktur der modulierten Phase wurde erstmals zuverlässig bestimmt, die Rolle des Li charakterisiert, Zweifel an der hexagonalen Symmetrie des ß-Eukryptits wurden ausgeräumt und die Bestimmung der modulierten Struktur wurde weitgehend vorbereitet.

The swelling behaviour of polyelectrolyte networks

Being basic ingredients of numerous daily-life products with significant industrial importance as well as basic building blocks for biomaterials, charged hydrogels continue to pose a series of unanswered challenges for scientists even after decades of practical applications and intensive research efforts. Despite a rather simple internal structure it is mainly the unique combination of short- and long-range forces which render scientific investigations of their characteristic properties to be quite difficult. Hence early on computer simulations were used to link analytical theory and empirical experiments, bridging the gap between the simplifying assumptions of the models and the complexity of real world measurements. Due to the immense numerical effort, even for high performance supercomputers, system sizes and time scales were rather restricted until recently, whereas it only now has become possible to also simulate a network of charged macromolecules. This is the topic of the presented thesis which investigates one of the fundamental and at the same time highly fascinating phenomenon of polymer research: The swelling behaviour of polyelectrolyte networks. For this an extensible simulation package for the research on soft matter systems, ESPResSo for short, was created which puts a particular emphasis on mesoscopic bead-spring-models of complex systems. Highly efficient algorithms and a consistent parallelization reduced the necessary computation time for solving equations of motion even in case of long-ranged electrostatics and large number of particles, allowing to tackle even expensive calculations and applications. Nevertheless, the program has a modular and simple structure, enabling a continuous process of adding new potentials, interactions, degrees of freedom, ensembles, and integrators, while staying easily accessible for newcomers due to a Tcl-script steering level controlling the C-implemented simulation core. Numerous analysis routines provide means to investigate system properties and observables on-the-fly. Even though analytical theories agreed on the modeling of networks in the past years, our numerical MD-simulations show that even in case of simple model systems fundamental theoretical assumptions no longer apply except for a small parameter regime, prohibiting correct predictions of observables. Applying a "microscopic" analysis of the isolated contributions of individual system components, one of the particular strengths of computer simulations, it was then possible to describe the behaviour of charged polymer networks at swelling equilibrium in good solvent and close to the Theta-point by introducing appropriate model modifications. This became possible by enhancing known simple scaling arguments with components deemed crucial in our detailed study, through which a generalized model could be constructed. Herewith an agreement of the final system volume of swollen polyelectrolyte gels with results of computer simulations could be shown successfully over the entire investigated range of parameters, for different network sizes, charge fractions, and interaction strengths. In addition, the "cell under tension" was presented as a self-regulating approach for predicting the amount of swelling based on the used system parameters only. Without the need for measured observables as input, minimizing the free energy alone already allows to determine the the equilibrium behaviour. In poor solvent the shape of the network chains changes considerably, as now their hydrophobicity counteracts the repulsion of like-wise charged monomers and pursues collapsing the polyelectrolytes. Depending on the chosen parameters a fragile balance emerges, giving rise to fascinating geometrical structures such as the so-called pear-necklaces. This behaviour, known from single chain polyelectrolytes under similar environmental conditions and also theoretically predicted, could be detected for the first time for networks as well. An analysis of the total structure factors confirmed first evidences for the existence of such structures found in experimental results.

Strukturbildungsverhalten kettensteifer Polyelektrolyte in wässrigen Lösungen am Beispiel von Poly(para-phenylen)sulfonat

An einer Vielzahl biogener Polyelektrolyte, wie z.B. den Nukleinsäuren DNA und RNA sowie Proteinen, ist die Ausbildung von Strukturhierarchien durch Selbstorganisation von Strukturelementen zu beobachten. Dabei wird das Strukturbildungsverhalten durch eine Kopplung von Wechselwirkungen auf verschiedenen Längenskalen, den kurzreichweitigen ausgeschlossenen Volumen und den langreichweitigen elektrostatischen Wechselwirkungen (Coulomb-Wechselwirkungen), die wiederum durch eine Vielzahl mikroskopische Parameter (z.B. Konformation) beeinflusst werden, bestimmt. Durch diese Komplexität ist es nicht möglich, den für die Strukturbildung hochgeladener Systeme bedeutsamen Beitrag der elektrostatischen Wechselwirkungen isoliert zu betrachten. Aus diesem Grund werden zur Aufklärung von Wechselwirkungs- und Strukturbildungsmechanismen vereinfachte Modell-Systeme herangezogen. Eine Möglichkeit besteht in der Verwendung synthetischer, kettensteifer Polyelektrolyte. Im Rahmen dieser Arbeit wurde das Aggregationsverhalten wässriger Lösungen dodecylsubstituierter Poly(para-phenylen)sulfonate (PPPS) sowie die Beeinflussung der Strukturbildung durch verschiedene Parameter charakterisiert. Als Einflussparameter wurden einerseits die Gegenion-Spezies und andererseits die Temperatur- und Konzentrations-Abhängigkeit untersucht. Hierzu wurden wässrige Lösungen der freien Säuren der PPPS mit Molekulargewichten zwischen MW = 18 kg/mol bis 58 kg/mol mittels Licht-, Röntgen- und Neutronenstreuung sowie durch Licht-, Polarisations-, Transmissionselektronen- und Rasterkraftmikroskopie in einem Konzentrationsbereich von 0,0008 < c < 1,1 g/L untersucht.

Tuning the structural and magnetic properties of Sr 2 FeReO 6 by substituting Fe and Re with valence invariant metals

In the course of this work the effect of metal substitution on the structural and magnetic properties of the double perovskites Sr2MM’O6 (M = Fe, substituted by Cr, Zn and Ga; M’ = Re, substituted by Sb) was explored by means of X-ray diffraction, magnetic measurements, band structure calculations, Mößbauer spectroscopy and conductivity measurements. The focus of this study was the determination of (i) the kind and structural boundary conditions of the magnetic interaction between the M and M’ cations and (ii) the conditions for the principal application of double perovskites as spintronic materials by means of the band model approach. Strong correlations between the electronic, structural and magnetic properties have been found during the study of the double perovskites Sr2Fe1-xMxReO6 (0 < x < 1, M = Zn, Cr). The interplay between van Hove-singularity and Fermi level plays a crucial role for the magnetic properties. Substitution of Fe by Cr in Sr2FeReO6 leads to a non-monotonic behaviour of the saturation magnetization (MS) and an enhancement for substitution levels up to 10 %. The Curie temperatures (TC) monotonically increase from 401 to 616 K. In contrast, Zn substitution leads to a continuous decrease of MS and TC. The diamagnetic dilution of the Fe-sublattice by Zn leads to a transition from an itinerant ferrimagnetic to a localized ferromagnetic material. Thus, Zn substitution inhibits the long-range ferromagnetic interaction within the Fe-sublattice and preserves the long-range ferromagnetic interaction within the Re-sublattice. Superimposed on the electronic effects is the structural influence which can be explained by size effects modelled by the tolerance factor t. In the case of Cr substitution, a tetragonal – cubic transformation for x > 0.4 is observed. For Zn substituted samples the tetragonal distortion linearly increases with increasing Zn content. In order to elucidate the nature of the magnetic interaction between the M and M’ cations, Fe and Re were substituted by the valence invariant main group metals Ga and Sb, respectively. X-ray diffraction reveals Sr2FeRe1-xSbxO6 (0 < x < 0.9) to crystallize without antisite disorder in the tetragonal distorted perovskite structure (space group I4/mmm). The ferrimagnetic behaviour of the parent compound Sr2FeReO6 changes to antiferromagnetic upon Sb substitution as determined by magnetic susceptibility measurements. Samples up to a doping level of 0.3 are ferrimagnetic, while Sb contents higher than 0.6 result in an overall antiferromagnetic behaviour. 57Fe Mößbauer results show a coexistence of ferri- and antiferromagnetic clusters within the same perovskite-type crystal structure in the Sb substitution range 0.3 < x < 0.8, whereas Sr2FeReO6 and Sr2FeRe0.9Sb0.1O6 are “purely” ferrimagnetic and Sr2FeRe0.1Sb0.9O6 contains antiferromagnetically ordered Fe sites only. Consequently, a replacement of the Re atoms by a nonmagnetic main group element such as Sb blocks the double exchange pathways Fe–O–Re(Sb)–O–Fe along the crystallographic axis of the perovskite unit cell and destroys the itinerant magnetism of the parent compound. The structural and magnetic characterization of Sr2Fe1-xGaxReO6 (0 < x < 0.7) exhibit a Ga/Re antisite disorder which is unexpected because the parent compound Sr2FeReO6 shows no Fe/Re antisite disorder. This antisite disorder strongly depends on the Ga content of the sample. Although the X-ray data do not hint at a phase separation, sample inhomogeneities caused by a demixing are observed by a combination of magnetic characterization and Mößbauer spectroscopy. The 57Fe Mößbauer data suggest the formation of two types of clusters, ferrimagnetic Fe- and paramagnetic Ga-based ones. Below 20 % Ga content, Ga statistically dilutes the Fe–O–Re–O–Fe double exchange pathways. Cluster formation begins at x = 0.2, for 0.2 < x < 0.4 the paramagnetic Ga-based clusters do not contain any Fe. Fe containing Ga-based clusters which can be detected by Mößbauer spectroscopy firstly appear for x = 0.4.

Spin polarised Heusler compounds

In der vorliegenden Dissertation dient ein einfaches Konzept zur Systematisierung der Suche nach neuen Materialien mit hoher Spinpolarisation. Dieses Konzept basiert auf zwei semi-empirischen Modellen. Zum einen kann die Slater-Pauling Regel zur Abschätzung magnetischer Momente verwendet werden. Dieses Modell wird dabei durch Rechnungen zur elektronischen Struktur unterstützt. Das zweites Modell kann insbesondere für die Co2YZ Heusler Verbindungen beim Vergleich ihrer magnetischen Eigenschaften gefunden werden. Für diese Verbindungen ergibt sich eine scheinbare lineare Abhängigkeit der Curie-Temperatur beim Auftragen als Funktion des magnetischen Momentes. Angeregt durch diese Modelle wurde die Heusler Verbindung Co2FeSi nochmals detailliert im Hinblick auf ihre geometrische und magnetische Struktur hin untersucht. Als Methoden dienten dabei die Pulver-Röntgenbeugung, die EXAFS Spektroskopie, Röntgen Absorptions- and Mößbauer Spektroskopie sowie Hoch- und Tieftemperatur Magnetometrie, XMCD and DSC. Die Messungen zeigten, dass es sich bei Co2FeSi um das Material mit dem höchsten magnetischen Moment (6 B) und der höchsten Curie Temperatur (1100 K) sowohl in der Klasse der Heusler Verbindungen als auch in der Klasse der halbmetallischen Ferromagnete handelt. Zusätzlich werden alle experimentellen Ergebnisse durch detaillierte Rechnungen zur elektronischen Struktur unterstützt. Die gleichen Konzepte wurden verwendet, um die Eigenschaften der Heusler Verbindung Co2Cr1-xFexAl vorherzusagen. Die elektronische Struktur und die spektroskopischen Eigenschaften wurden mit der voll-relativistischen Korringa-Kohn-Rostocker Methode berechnet, unter Verwendung kohärenter Potentialnäherungen um der zufälligen Verteilung von Cr und Fe Atomen sowie zufälliger Unordnung Rechnung zu tragen. Magnetische Effekte wurden durch die Verwendung Spin-abhängiger Potentiale im Rahmen der lokalen Spin-Dichte-Näherung mit eingeschlossen. Die strukturellen und chemischen Eigenschaften der quaternären Heusler Verbindung Co2Cr1-xFexAl wurden an Pulver und Bulkproben gemessen. Die Fernordnung wurde mit der Pulver Röntgenbeugung und Neutronenbeugung untersucht, während die Nahordnung mit der EXAFS Spektroskopie aufgeklärt wurde. Die magnetische Struktur von Pulver und Bulkproben wurde mitttels 57Fe-Mößbauer Spektroskopie gemessen. Die chemische Zusammensetzung wurde durch XPS analysiert. Die Ergebnisse dieser Methoden wurden verglichen, um eine Einsicht in die Unterschiede zwischen Oberflächen und Volumeneigenschaften zu erlangen sowie in das Auftreten von Fehlordnung in solchen Verbindungen. Zusätzlich wurde XMCD an den L3,2 Kanten von Co, Fe, and Cr gemessen, um die elementspezifischen magnetischen Momente zu bestimmen. Rechnungen und Messungen zeigen dabei eine Zunahme des magnetischen Momentes bei steigendem Fe-Anteil. Resonante Photoemission mit weicher Röntgenstrahlung sowie Hochenergie Photoemission mit harter Röntgenstrahlung wurden verwendet, um die Zustandsdichte der besetzten Zustände in Co2Cr0.6Fe0.4Al zu untersuchen. Diese Arbeit stellt außerdem eine weitere, neue Verbindung aus der Klasse der Heusler Verbindungen vor. Co2CrIn ist L21 geordnet, wie Messungen mittels Pulver Röntgenbeugung zeigen. Die magnetischen Eigenschaften wurden mit magnetometrisch bestimmt. Co2CrIn ist weichmagnetisch mit einer Sättigungsmagnetisierung von 1.2B bei 5 K. Im Gegensatz zu den bereits oben erwähnten Co2YZ Heusler Verbindungen ist Co2CrIn kein halbmetallischer Ferromagnet. Im Rahmen dieser Arbeit wird weiterhin eine Regel zur Vorhersage von halbmetallischen komplett kompensierten Ferrimagneten in der Klasse der Heusler Verbindungen vorgestellt. Dieses Konzept resultiert aus der Kombination der Slater-Pauling Regel mit der Kübler-Regel. Die Kübler Regel besagt, dass Mn auf der Y Position zu einem hoch lokalisierten magnetischen Moment tendiert. Unter Verwendung dieses neuen Konzeptes werden für einige Kandidaten in der Klasse der Heusler Verbindungen die Eigenschaft des halbmetallischen komplett kompensierten Ferrimagnetismus vorhergesagt. Die Anwendung dieses Konzeptes wird anhand von Rechnungen zur elektronischen Struktur bestätigt.

Computer simulations of two-dimensional colloidal crystals in confinement

Monte Carlo simulations are used to study the effect of confinement on a crystal of point particles interacting with an inverse power law potential in d=2 dimensions. This system can describe colloidal particles at the air-water interface, a model system for experimental study of two-dimensional melting. It is shown that the state of the system (a strip of width D) depends very sensitively on the precise boundary conditions at the two ``walls'' providing the confinement. If one uses a corrugated boundary commensurate with the order of the bulk triangular crystalline structure, both orientational order and positional order is enhanced, and such surface-induced order persists near the boundaries also at temperatures where the system in the bulk is in its fluid state. However, using smooth repulsive boundaries as walls providing the confinement, only the orientational order is enhanced, but positional (quasi-) long range order is destroyed: The mean-square displacement of two particles n lattice parameters apart in the y-direction along the walls then crosses over from the logarithmic increase (characteristic for $d=2$) to a linear increase (characteristic for d=1). The strip then exhibits a vanishing shear modulus. These results are interpreted in terms of a phenomenological harmonic theory. Also the effect of incommensurability of the strip width D with the triangular lattice structure is discussed, and a comparison with surface effects on phase transitions in simple Ising- and XY-models is made