Adsorption of element 112 on a Au surface

Während der letzten 20 Jahre hat sich das Periodensystem bis zu den Elementen 114 und 116 erweitert. Diese sind kernphysikalisch nachgewiesen, so dass jetzt die chemische Untersuchung an erster Selle steht. Nachdem sich das Periodensystem bis zum Element 108 so verhält, wie man es dem Periodensystem nach annimmt, wird in dieser Arbeit die Chemie des Elements 112 untersucht. Dabei geht es um die Adsorptionsenergie auf einer Gold-Ober fläche, weil dies der physikalisch/chemische Prozess ist, der bei der Analyse angewandt wird. Die Methode, die in dieser Arbeit angwandt wird, ist die relativistische Dichtefunktionalmethode. Im ersten Teil wird das Vielkörperproblem in allgemeiner Form behandelt, und im zweiten die grundlegenden Eigenschaften und Formulierungen der Dichtefunktionaltheorie. Die Arbeit beschreibt zwei prinzipiell unterschiedliche Ansätze, wie die Adsorptionsenergie berechnet werden kann. Zum einen ist es die sogenannte Clustermethode, bei der ein Atom auf ein relativ kleines Cluster aufgebracht und dessen Adsorptionsenergie berechnet wird. Wenn es gelingt, die Konvergenz mit der Größe des Clusters zu erreichen, sollte dies zu einem Wert für die Adsorptionsenergie führen. Leider zeigt sich in den Rechnungen, dass aufgrund des zeitlichen Aufwandes die Konvergenz für die Clusterrechnungen nicht erreicht wird. Es werden sehr ausführlich die drei verschiedenen Adsorptionsplätze, die Top-, die Brücken- und die Muldenposition, berechnet. Sehr viel mehr Erfolg erzielt man mit der Einbettungsmethode, bei der ein kleiner Cluster von vielen weiteren Atomen an den Positionen, die sie im Festkörpers auf die Adsorptionsenergie soweit sichergestellt ist, dass physikalisch-chemisch gute Ergebnisse erzielt werden. Alle hier gennanten Rechnungen sowohl mit der Cluster- wie mit der Einbettungsmethode verlangen sehr, sehr lange Rechenzeiten, die, wie oben bereits erwähnt, nicht zu einer Konvergenz für die Clusterrechnungen ausreichten. In der Arbeit wird bei allen Rechnungen sehr detailliert auf die Abhängigkeit von den möglichen Basissätzen eingegangen, die ebenfalls in entscheidender Weise zur Länge und Qualität der Rechnungen beitragen. Die auskonvergierten Rechnungen werden in der Form von Potentialkurven, Density of States (DOS), Overlap Populations sowie Partial Crystal Overlap Populations analysiert. Im Ergebnis zeigt sich, dass die Adsoptionsenergie für das Element 112 auf einer Goldoberfläche ca. 0.2 eV niedriger ist als die Adsorption von Quecksilber auf der gleichen Ober fläche. Mit diesem Ergebnis haben die experimentellen Kernchemiker einen Wert an der Hand, mit dem sie eine Anhaltspunkt haben, wo sie bei den Messungen die wenigen zu erwartenden Ereignisse finden können.

Architecture and other Architectures: Mapping the Production of Insular Space in the Pearl River Delta (China) and Jakarta (Indonesia)

Globalization is widely regarded as the rise of the borderless world. However in practice, true globalization points rather to a “spatial logic” by which globalization is manifested locally in the shape of insular space. Globalization in this sense is not merely about the creation of physical fragmentation of space but also the creation of social disintegration. This study tries to proof that global processes also create various forms of insular space leading also to specific social implications. In order to examine the problem this study looks at two cases: China’s Pearl River Delta (PRD) and Jakarta in Indonesia. The PRD case reveals three forms of insular space namely the modular, concealed and the hierarchical. The modular points to the form of enclosed factories where workers are vulnerable for human-right violations due to the absent of public control. The concealed refers to the production of insular space by subtle discrimination against certain social groups in urban space. And the hierarchical points to a production of insular space that is formed by an imbalanced population flow. The Jakarta case attempts to show more types of insularity in relation to the complexity of a mega-city which is shaped by a culture of exclusion. Those are dormant and hollow insularity. The dormant refers to the genesis of insular– radical – community from a culture of resistance. The last type, the hollow, points to the process of making a “pseudo community” where sense of community is not really developed as well as weak social relationship with its surrounding. Although global process creates various expressions of territorial insularization, however, this study finds that the “line of flight” is always present, where the border of insularity is crossed. The PRD’s produces vernacular modernization done by peasants which is less likely to be controlled by the politics of insularization. In Jakarta, the culture of insularization causes urban informalities that have no space, neither spatially nor socially; hence their state of ephemerality continues as a tactic of place-making. This study argues that these crossings possess the potential for reconciling venue to defuse the power of insularity.

The Surface Plasmon Resonance of Supported Noble Metal Nanoparticles: Characterization, Laser Tailoring, and SERS Application

This work deals with the optical properties of supported noble metal nanoparticles, which are dominated by the so-called Mie resonance and are strongly dependent on the particles’ morphology. For this reason, characterization and control of the dimension of these systems are desired in order to optimize their applications. Gold and silver nanoparticles have been produced on dielectric supports like quartz glass, sapphire and rutile, by the technique of vapor deposition under ultra-high vacuum conditions. During the preparation, coalescence is observed as an important mechanism of cluster growth. The particles have been studied in situ by optical transmission spectroscopy and ex situ by atomic force microscopy. It is shown that the morphology of the aggregates can be regarded as oblate spheroids. A theoretical treatment of their optical properties, based on the quasistatic approximation, and its combination with results obtained by atomic force microscopy give a detailed characterization of the nanoparticles. This method has been compared with transmission electron microscopy and the results are in excellent agreement. Tailoring of the clusters’ dimensions by irradiation with nanosecond-pulsed laser light has been investigated. Selected particles are heated within the ensemble by excitation of the Mie resonance under irradiation with a tunable laser source. Laser-induced coalescence prevents strongly tailoring of the particle size. Nevertheless, control of the particle shape is possible. Laser-tailored ensembles have been tested as substrates for surface-enhanced Raman spectroscopy (SERS), leading to an improvement of the results. Moreover, they constitute reproducible, robust and tunable SERS-substrates with a high potential for specific applications, in the present case focused on environmental protection. Thereby, these SERS-substrates are ideally suited for routine measurements.

Molecular Beam Epitaxial Growth of III-V Semiconductor Nanostructures on Silicon Substrates

The main focus and concerns of this PhD thesis is the growth of III-V semiconductor nanostructures (Quantum dots (QDs) and quantum dashes) on silicon substrates using molecular beam epitaxy (MBE) technique. The investigation of influence of the major growth parameters on their basic properties (density, geometry, composition, size etc.) and the systematic characterization of their structural and optical properties are the core of the research work. The monolithic integration of III-V optoelectronic devices with silicon electronic circuits could bring enormous prospect for the existing semiconductor technology. Our challenging approach is to combine the superior passive optical properties of silicon with the superior optical emission properties of III-V material by reducing the amount of III-V materials to the very limit of the active region. Different heteroepitaxial integration approaches have been investigated to overcome the materials issues between III-V and Si. However, this include the self-assembled growth of InAs and InGaAs QDs in silicon and GaAx matrices directly on flat silicon substrate, sitecontrolled growth of (GaAs/In0,15Ga0,85As/GaAs) QDs on pre-patterned Si substrate and the direct growth of GaP on Si using migration enhanced epitaxy (MEE) and MBE growth modes. An efficient ex-situ-buffered HF (BHF) and in-situ surface cleaning sequence based on atomic hydrogen (AH) cleaning at 500 °C combined with thermal oxide desorption within a temperature range of 700-900 °C has been established. The removal of oxide desorption was confirmed by semicircular streaky reflection high energy electron diffraction (RHEED) patterns indicating a 2D smooth surface construction prior to the MBE growth. The evolution of size, density and shape of the QDs are ex-situ characterized by atomic-force microscopy (AFM) and transmission electron microscopy (TEM). The InAs QDs density is strongly increased from 108 to 1011 cm-2 at V/III ratios in the range of 15-35 (beam equivalent pressure values). InAs QD formations are not observed at temperatures of 500 °C and above. Growth experiments on (111) substrates show orientation dependent QD formation behaviour. A significant shape and size transition with elongated InAs quantum dots and dashes has been observed on (111) orientation and at higher Indium-growth rate of 0.3 ML/s. The 2D strain mapping derived from high-resolution TEM of InAs QDs embedded in silicon matrix confirmed semi-coherent and fully relaxed QDs embedded in defectfree silicon matrix. The strain relaxation is released by dislocation loops exclusively localized along the InAs/Si interfaces and partial dislocations with stacking faults inside the InAs clusters. The site controlled growth of GaAs/In0,15Ga0,85As/GaAs nanostructures has been demonstrated for the first time with 1 μm spacing and very low nominal deposition thicknesses, directly on pre-patterned Si without the use of SiO2 mask. Thin planar GaP layer was successfully grown through migration enhanced epitaxy (MEE) to initiate a planar GaP wetting layer at the polar/non-polar interface, which work as a virtual GaP substrate, for the GaP-MBE subsequently growth on the GaP-MEE layer with total thickness of 50 nm. The best root mean square (RMS) roughness value was as good as 1.3 nm. However, these results are highly encouraging for the realization of III-V optical devices on silicon for potential applications.

Extracting Urban Food Potential: design-based methods for digital and bodily cartography

Sweden’s recent report on Urban Sustainable Development calls out a missing link between the urban design process and citizens. This paper investigates if engaging citizens as design agents by providing a platform for alternate participation can bridge this gap, through the transfer of spatial agency and new modes of critical cartography. To assess whether this is the case, the approaches are applied to Stockholm’s urban agriculture movement in a staged intervention. The aim of the intervention was to engage citizens in locating existing and potential places for growing food and in gathering information from these sites to inform design in urban agriculture. The design-based methodologies incorporated digital and bodily interfaces for this cartography to take place. The Urban CoMapper, a smartphone digital app, captured real-time perspectives through crowd-sourced mapping. In the bodily cartography, participant’s used their bodies to trace the site and reveal their sensorial perceptions. The data gathered from these approaches gave way to a mode of artistic research for exploring urban agriculture, along with inviting artists to be engaged in the dialogues. In sum, results showed that a combination of digital and bodily approaches was necessary for a critical cartography if we want to engage citizens holistically into the urban design process as spatial agents informing urban policy. Such methodologies formed a reflective interrogation and encouraged a new intimacy with nature, in this instance, one that can transform our urban conduct by questioning our eating habits: where we get our food from and how we eat it seasonally.

Heat stress response for physiological traits in dairy and dual purpose cattle populations on phenotypic and genetic scales

The main objective of this thesis was to determine the potential impact of heat stress (HS) on physiological traits of lactating cows and semen quality of bulls kept in a temperate climate. The thesis is comprised of three studies. An innovative statistical modeling aspect common to all three studies was the application of random regression methodology (RRM) to study the phenotypic and genetic trajectory of traits in dependency of a continuous temperature humidity index (THI). In the first study, semen quality and quantity traits of 562 Holstein sires kept on an AI station in northwestern Germany were analyzed in the course of THI calculated from data obtained from the nearest weather station. Heat stress was identified based on a decline in semen quality and quantity parameters. The identified general HS threshold (THI = 60) and the thermoneutal zone (THI in the range from 50 to 60) for semen production were lower than detected in studies conducted in tropical and subtropical climates. Even though adult bulls were characterized by higher semen productivity compared to younger bulls, they responded with a stronger semen production loss during harsh environments. Heritabilities (low to moderate range) and additive genetic variances of semen characteristics varied with different levels of THI. Also, based on genetic correlations genotype, by environment interactions were detected. Taken together, these findings suggest the application of specific selection strategies for specific climate conditions. In the second study, the effect of the continuous environmental descriptor THI as measured inside the barns on rectal temperatures (RT), skin temperatures (ST), vaginal temperatures (VT), respiration rates (RR), and pulse rate (PR) of lactating Holstein Friesian (HF) and dual-purpose German black pied cattle (DSN) was analyzed. Increasing HS from THI 65 (threshold) to THI 86 (maximal THI) resulted in an increase of RT by 0.6 °C (DSN) and 1 °C (HF), ST by 3.5 °C (HF) and 8 °C (DSN), VT by 0.3 °C (DSN), and RR by 47 breaths / minute (DSN), and decreased PR by 7 beats / minute (DSN). The undesired effects of rising THI on physiological traits were most pronounced for cows with high levels of milk yield and milk constituents, cows in early days in milk and later parities, and during summer seasons in the year 2014. In the third study of this dissertation, the genetic components of the cow’s physiological responses to HS were investigated. Heat stress was deduced from indoor THI measurements, and physiological traits were recorded on native DSN cows and their genetically upgraded crosses with Holstein Friesian sires in two experimental herds from pasture-based production systems reflecting a harsh environment of the northern part of Germany. Although heritabilities were in a low range (from 0.018 to 0.072), alterations of heritabilities, repeatabilities, and genetic components in the course of THI justify the implementation of genetic evaluations including heat stress components. However, low repeatabilities indicate the necessity of using repeated records for measuring physiological traits in German cattle. Moderate EBV correlations between different trait combinations indicate the potential of selection for one trait to simultaneously improve the other physiological attributes. In conclusion, bulls of AI centers and lactating cows suffer from HS during more extreme weather conditions also in the temperate climate of Northern Germany. Monitoring physiological traits during warm and humid conditions could provide precious information for detection of appropriate times for implementation of cooling systems and changes in feeding and management strategies. Subsequently, the inclusion of these physiological traits with THI specific breeding values into overall breeding goals could contribute to improving cattle adaptability by selecting the optimal animal for extreme hot and humid conditions. Furthermore, the recording of meteorological data in close distance to the cow and visualizing the surface body temperature by infrared thermography techniques might be helpful for recognizing heat tolerance and adaptability in cattle.

Transport magnetischer Partikel durch maßgeschneiderte magnetische Feldlandschaften zur Anwendung in mikrofluidischen Mischprozessen

Die Miniaturisierung von konventioneller Labor- und Analysetechnik nimmt eine zentrale Rolle im Bereich der allgemeinen Lebenswissenschaften und medizinischen Diagnostik ein. Neuartige und preiswerte Technologieplattformen wie Lab-on-a-Chip (LOC) oder Mikrototalanalysesysteme (µTAS) versprechen insbesondere im Bereich der Individualmedizin einen hohen gesellschaftlichen Nutzen zur frühzeitigen und nichtinvasiven Diagnose krankheitsspezifischer Indikatoren. Durch den patientennahen Einsatz preiswerter und verlässlicher Mikrochips auf Basis hoher Qualitätsstandards entfallen kostspielige und zeitintensive Zentrallaboranalysen, was gleichzeitig Chancen für den globalen Einsatz - speziell in Schwellen- und Entwicklungsländern - bietet. Die technischen Herausforderungen bei der Realisierung moderner LOC-Systeme sind in der kontrollierten und verlässlichen Handhabung kleinster Flüssigkeitsmengen sowie deren diagnostischem Nachweis begründet. In diesem Kontext wird der erfolgreichen Integration eines fernsteuerbaren Transports von biokompatiblen, magnetischen Mikro- und Nanopartikeln eine Schlüsselrolle zugesprochen. Die Ursache hierfür liegt in der vielfältigen Einsetzbarkeit, die durch die einzigartigen Materialeigenschaften begründet sind. Diese reichen von der beschleunigten, aktiven Durchmischung mikrofluidischer Substanzvolumina über die Steigerung der molekularen Interaktionsrate in Biosensoren bis hin zur Isolation und Aufreinigung von krankheitsspezifischen Indikatoren. In der Literatur beschriebene Ansätze basieren auf der dynamischen Transformation eines makroskopischen, zeitabhängigen externen Magnetfelds in eine mikroskopisch veränderliche potentielle Energielandschaft oberhalb magnetisch strukturierter Substrate, woraus eine gerichtete und fernsteuerbare Partikelbewegung resultiert. Zentrale Kriterien, wie die theoretische Modellierung und experimentelle Charakterisierung der magnetischen Feldlandschaft in räumlicher Nähe zur Oberfläche der strukturierten Substrate sowie die theoretische Beschreibung der Durchmischungseffekte, wurden jedoch bislang nicht näher beleuchtet, obwohl diese essentiell für ein detailliertes Verständnis der zu Grunde liegenden Mechanismen und folglich für einen Markteintritt zukünftiger Geräte sind. Im Rahmen der vorgestellten Arbeit wurde daher ein neuartiger Ansatz zur erfolgreichen Integration eines Konzepts zum fernsteuerbaren Transport magnetischer Partikel zur Anwendung in modernen LOC-Systemen unter Verwendung von magnetisch strukturierten Exchange-Bias (EB) Dünnschichtsystemen verfolgt. Die Ergebnisse zeigen, dass sich das Verfahren der ionenbe-schussinduzierten magnetischen Strukturierung (IBMP) von EB-Systemen zur Herstellung von maßgeschneiderten magnetischen Feldlandschaften (MFL) oberhalb der Substratoberfläche, deren Stärke und räumlicher Verlauf auf Nano- und Mikrometerlängenskalen gezielt über die Veränderung der Materialparameter des EB-Systems via IBMP eingestellt werden kann, eignet. Im Zuge dessen wurden erstmals moderne, experimentelle Verfahrenstechniken (Raster-Hall-Sonden-Mikroskopie und rastermagnetoresistive Mikroskopie) in Kombination mit einem eigens entwickelten theoretischen Modell eingesetzt, um eine Abbildung der MFL in unterschiedlichen Abstandsbereichen zur Substratoberfläche zu realisieren. Basierend auf der quantitativen Kenntnis der MFL wurde ein neuartiges Konzept zum fernsteuerbaren Transport magnetischer Partikel entwickelt, bei dem Partikelgeschwindigkeiten im Bereich von 100 µm/s unter Verwendung von externen Magnetfeldstärken im Bereich weniger Millitesla erzielt werden können, ohne den magnetischen Zustand des Substrats zu modifizieren. Wie aus den Untersuchungen hervorgeht, können zudem die Stärke des externen Magnetfelds, die Stärke und der Gradient der MFL, das magnetfeldinduzierte magnetische Moment der Partikel sowie die Größe und der künstlich veränderliche Abstand der Partikel zur Substratoberfläche als zentrale Einflussgrößen zur quantitativen Modifikation der Partikelgeschwindigkeit genutzt werden. Abschließend wurde erfolgreich ein numerisches Simulationsmodell entwickelt, das die quantitative Studie der aktiven Durchmischung auf Basis des vorgestellten Partikeltransportkonzepts von theoretischer Seite ermöglicht, um so gezielt die geometrischen Gegebenheiten der mikrofluidischen Kanalstrukturen auf einem LOC-System für spezifische Anwendungen anzupassen.