Luminescent organic materials with high photostability are essential in optoelectronics, sensor, and photocatalysis applications. However, small organic molecules are generally sensitive to UV irradiation, giving rise to chemical decompositions. In this work, we demonstrate two novel CN-substituted two-dimensional sp²-carbon-linked conjugated polymers (2D CCPs) containing a chromophore triphenylene unit. The Knoevenagel polymerization between 2,3,6,7,10,11-hexakis(4-formylphenyl)triphenylene (HFPTP) and 1,4-phenylenediacetonitrile (PDAN) or 2,2’-(biphenyl-4,4’-diyl)diacetonitrile (BDAN), provides the crystalline 2D CCP-HFPTP-PDAN (2D CCP-1) and 2D CCP-HFPTP-BDAN (2D CCP-2) with dual pore structures, respectively. 2D CCP-1 and 2D CCP-2 exhibit the photoluminescence quantum yield (PLQY) up to 24.9% and 32.3%, which are the highest values among the reported 2D conjugated polymers and π-conjugated 2D covalent organic frameworks. Furthermore, compared with the well-known emissive small molecule tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), both 2D CCPs show superior photostability under UV irradiation for two hours, profiting from the twisted and rigid structures of the CN-substituted vinylene linkages. The present work will trigger the further explorations of novel organic emitters embedded in 2D CCPs with high PLQY and photostability, which can be useful for optoelectronic devices.

Im theoretischen Teil der Arbeit wird zunächst ein Überblick über die innere Struktur amorpher Spritzgußteile und die Theorie des freien Volumens gegeben. Es wird auf die Abhängigkeit der Relaxationszeiten von dem im Werkstoff vorhandenen Leerstellenvolumen (freien Volumen) bei Änderung der Temperatur, der Abkühlrate, der Alterungszeit und des Druckes sowie auf das Phänomen der Druckverdichtung eingegangen. Es wird untersucht, welche Bedeutung dem freien Volumen hinsichtlich des Deformationsverhaltens spritzgegossener amorpher Thermoplaste zukommt und inwieweit dessen Effekt bei den für die Praxis interessanten Spritzgußteilen unter Umständen durch andere Einflußgrößen wie Orientierungen und Eigenspannungen überdeckt wird. Betrachtet wird der Einfluß verschiedener Verarbeitungsparameter, der Formteildicke und der physikalischen Alterung (Zeit zwischen Verarbeitung und Prüfung der Spritzgußteile bzw. Tempern unterhalb der Glastemperatur) auf die innere Struktur des Kunststoffes und dessen Auswirkungen auf das resultierende Deformationsverhalten.

In algorithmic computing, the program follows a predefined set of rules – the algorithm. The analyst/designer of the program analyzes the intended tasks of the program, defines the rules for its expected behaviour and programs the implementation. The creators of algorithmic software must therefore foresee, identify and implement all possible cases for its behaviour in the future application! However, what if the problem is not fully defined? Or the environment is uncertain? What if situations are too complex to be predicted? Or the environment is changing dynamically? In many such cases algorithmic computing fails. In such situations, the software needs an additional degree of freedom: Autonomy! Autonomy allows software to adapt to partially defined problems, to uncertain or dynamically changing environments and to situations that are too complex to be predicted. As more and more applications – such as autonomous cars and planes, adaptive power grid management, survivable networks, and many more – fall into this category, a gradual switch from algorithmic computing to autonomic computing takes place. Autonomic computing has become an important software engineering discipline with a rich literature, an active research community, and a growing number of applications.:Introduction 5 1 A Process Data Based Autonomic Optimization of Energy Efficiency in Manufacturing Processes, Daniel Höschele 9 2 Eine autonome Optimierung der Stabilität von Produktionsprozessen auf Basis von Prozessdaten, Richard Horn 25 3 Assuring Safety in Autonomous Systems, Christian Rose 41 4 MAPE-K in der Praxis - Grundlage für eine mögliche automatische Ressourcenzuweisung, in der Cloud Michael Schneider 59

The majority of bacteria are organized in surface-associated communities, the so called biofilms. Crucial processes that drive the formation of such biofilms are the motility of bacteria on a substrate, enabling cells to reach each others vicinity, and attractive cell-cell-interactions, driving the formation of microcolonies. These colonies, aggregates consisting of thousands of cells, are the precursors of biofilms. In this thesis we investigate the role of cell appendages, called type IV pili, in the substrate motion of bacteria and the formation of bacterial microcolonies. Therefore, we study the bacterial dynamics with the help of experiments and theoretical models. We introduce a novel simulation tool in the tradition of Brownian dynamics simulations. In this computational model, that was developed alongside experimental observations, we study how explicit pili dynamics, pili-substrate and pili–pili interactions drive the cell dynamics. First, we apply our model to investigate how individual cells move on a substrate due to cycles of protrusion and retraction of type IV pili. We show that the characteristic features, in particular persistent motion, can solely originate from collective interactions of pili. Next, we perform experiments to study the coalescence of bacterial microcolonies. With the help of experiments and our computational model, we identify a spatially-dependent gradient of motility of cells within the colony as the origin of a separation of time scale, a feature which is in disagreement with the coalescence dynamics of fluid droplets. Additionally, we show that altering the force generation of pili can cause demixing of cells within bacterial aggregates. Finally, we combine our knowledge of the substrate motion of cells and of the pili-mediated interactions of colonies to identify the main processes (aggregation, fragmentation and cell divisions) that drive assembly of colonies. Starting from experiments, we develop a mathematical model and observe excellent qualitative and quantitative agreement to experimental data of the density of colonies of different sizes. In summary, hand in hand with experiments, we develop theoretical frameworks to unravel the role of type IV pili in bacterial surface motility, microcolony dynamics and colony formation.:1. Introduction 2. Computational model of bacterial motility and mechanics 3. Motility of single bacteria on a substrate 4. Coalescence and internal dynamics of bacterial microcolonies 5. Demixing of bacterial microcolonies 6. Self-assembly of microcolonies 7. Summary and Outlook A. Details of the Simulation model B. Experimental protocols C. Geometric estimation of the parameters of the stochastic model D. Solutions for simplified models of pili-mediated cell motion E. Image analysis of experimental data F. Simulations and data analysis G. The mean squared relative distance (MSRD)

Stem cells are crucial players during development, homeostasis and tissue regeneration and their interactions with the surrounding microenvironment are key to regulate stem cell fate. The skull's stem cell niches reside in the fibrous joints that connect flat bones of the skull. In the embryo, bone and sutures develop in concert to form a complex, multi-facted structure that requires interaction with multiple differentiating cell types to maintain balance between growth and differentiation. Disruption of this balance drives changes in size and shape of skull bones and can severely impact quality of life. Cranial sutures, often seen as simple extracellular matrix-rich structures bridging the rigid plates of the skull, are major actors in craniofacial morphogenesis of as they harmonize bone growth with expansion of the developing brain and participate in providing osteoblasts during repair. The complexity of the extracellular environment and the important role for sutures in skeletal development makes these niches a compelling structure to investigate how interactions with the surrounding microenvironment can modulate stem cells fate. The key role of sutures in development is highlighted by the numerous severe dysmorphisms arising from failure to maintain suture patency. The ability of the suture to respond to brain growth or trauma and the dysmophisms presented by patients with defective sutures is mediated by both biochemical and mechanical cues but the cell biology of these niches remains elusive, especially during their development. In particular, few studies have shed light on the underlying cellular behaviors behind microenvironmental regulation of cranial suture stem cell fate and what role mechanical inputs play in the establishment of this niche. In my thesis, I addressed gaps in our understanding of suture biology by characterizing the suture stem cell niche microenvironment and exploring how cell-ECM interactions serve as regulators of suture stem cell fate. Making use of various microscopy and analytical techniques I first characterized the composition of the microenvironment in a developing suture niche, such as organization of ECM, cytoskeleton and nuclear morphologies. My work builds on an incomplete transcriptional understanding of suture cell development, such that specific genetic markers are rarely useful for identifying distinct suture cell populations during its morphogenesis. By applying shape description tools to parse suture cells and test whether shape correlates to cell identity, we concluded that suture nuclei are distinct and less spherical than those of other cranial tissues. Using 'global' markers such as nuclear stains, I have also identified physical distinctions between suture nuclei and neighboring tissues, indicating that cell shape is an integral part of midline suture identity and can be used to explore coordination of fate choice and morphogenesis in this enigmatic structure. In addition, I present evidence that supports that maturation of extracellular matrix begins during early stages of suture development. In particular, embryonic midline sutures express high levels of fibrillary collagen, which contributes to the formation of a complex extracellular environment that provides the suture with physical properties distinct from those of developing bones. My work shows the presence of cell-ECM and cell-cell adhesions in the developing midline sutures, as well as a complex actin cytoskeleton that is, in part, mediated by physical stresses resultant from underlying brain expansion. Secondly, I aimed to address how perturbations in ECM composition can affect cell specification. To investigate the importance of ECM maturation in regulating suture cell fate I inhibited the function of lysyl oxidase, a collagen crosslinker, during embryonic development. Disruption of collagen crosslinking altered expression of collagen and ECM receptor encoding genes. In addition, this inhibition induced changes in the shape and size of collagen fibers in the embryonic midline suture and decreased tissue bulk stiffness relative to WT. These abnormal properties of the ECM impact tissue delineation in the cranial mesenchyme through nuclear shape analyses. This might be explained by observed changes in the composition of the nuclear envelop of suture cells as we find altered lamin concentration and localization upon lysyl oxidase inhibition. The work developed during myPhD steps away from the traditional genetic approaches used to study the embryonic suture and provides the first in-depth analysis of the physical properties of the developing midline suture at stages preceding known establishment of the niche. The various methods and analyses applied reveal a complex organization of embryonic suture ECM and its tight relationship with shape and fate in this tissue. This work serves as a foundation for future studies that can explore the mechanisms through which ECM regulates fate and development of the suture niche, and potentially skeletal development more generally.

Die Mechanochemie findet zunehmend Verwendung für die Synthese neuer Verbindungen. Dennoch sind die beim Mahlen stattfindenden Prozesse weitestgehend unverstanden. Dahingehend wurde in dieser Arbeit eine Dreifachkopplung aus in situ Synchrotron-Röntgenbeugung, Raman-Spektroskopie und Thermographie entwickelt, um mechanochemische Reaktionen unter realistischen Bedingungen in Echtzeit zu verfolgen. Dadurch konnten tiefgreifende Einblicke in den Reaktionsverlauf und Temperaturverlauf beim Mahlen erhalten und neue metastabile Verbindungen isoliert werden. Für die Bildung pharmazeutischer Cokristalle diente Pyrazinamid als Modellsystem. Es konnten neue binäre und ternäre Verbindungen synthetisiert, detailliert charakterisiert und deren Kristallstruktur aufgeklärt werden. Die Abhängigkeit der Stabilität polymorpher Cokristalle von der Temperatur und den Synthesebedingungen konnte gezeigt werden. In Konkurrenzreaktionen konnten Trends hinsichtlich der bevorzugten Bildung eine bestimmten Cokristalls beobachtet werden. Mittels in situ Untersuchungen wurde der Einfluss zentraler Reaktionsparameter, wie die Mahlfrequenz, der Kugeldurchmesser, der eingesetzte Ausgangsstoff und die Zugabe von Lösungsmittel, auf die Induktions- und Reaktionszeit der Reaktion ermittelt. Basierend auf den gewonnenen Erkenntnissen konnte ein Diffusionsmechanismus für die mechanochemische Cokristallbildung abgeleitet werden. / Mechanochemistry is increasingly applied for the synthesis of new compounds. Still, the processes taking place during milling are far from being understood. In this thesis, a triple coupling of in situ synchrotron X-ray diffraction, Raman spectroscopy and thermography has been developed to follow mechanochemical reactions under realistic conditions in real time. This allowed deep insights into the reaction and temperature progression during milling and the isolation of new metastable compounds. For the formation of pharmaceutical cocrystals pyrazinamide served as a model system. New binary and ternary compounds were synthesized, characterized in detail and their crystal structure solved. The dependence of the stability of polymorphic cocrystals on temperature and synthesis conditions could be shown. In competitive reactions, trends regarding the preferred formation of a certain cocrystal have been observed. The influence of important reaction parameters, such as the milling frequency, the ball diameter, the starting material used and the addition of solvent, on the induction and reaction time of the reaction was determined by means of in situ investigations. Based on the gained knowledge, a diffusion mechanism for the mechanochemical cocrystal formation could be derived.

As former studies reveal, the nanoporous confinement could have influence on polymorphic drug crystallization. However, little attention has been paid to the question how crystallization of the commonly polymorphic drugs in nanoporous matrices influences the drug release. As a consequence, sufficient information about the crystallization conditions and their influence on phase behavior, crystal texture, and stability of polymorphs should be retrieved prior to drug delivery experiments. Drug release should be polymorph-selective and even crystal face-specific. Therefore, the topic of this PhD thesis is the systematic investigation of crystallization parameters (e.g., pore morphology, thermal history, presence or absence of a bulk surface reservoir) and their influence on the nucleation and crystal growth of the two selected model compounds in nanoporous matrices: acetaminophen (ACE) and n-tetracosane. Both are confined to two host-systems: AAO containing aligned cylindrical, isolated pores and CPG containing curved, interconnected pores. The guest materials inside the two model matrices have been investigated with X-ray diffraction (WAXS) and differential scanning calorimetry. In the first part it is shown that the nanopore morphology of the host systems determines into which polymorphic form ACE crystallizes. Moreover, the pore morphology influences the kinetics of solid/solid transitions. In AAO uniformly oriented form III crystals are converted into also uniformly oriented form II crystals by a solid/solid transition. Such a phase transition is kinetically suppressed in CPG membranes due to the curved pore morphology. In the second step, polymorph-specific release experiments with ACE from AAO membranes reveal that the drug dissolution is not exclusively diffusion-limited and can be described by the Korsmeyer-Peppas model. Dissolution of crystalline ACE having rough crystal faces exposed to the environment is nearly as fast as release of amorphous ACE. Encapsulating of ACE in AAO nanopores with a PLLA polymer retard the drug dissolution but does not modify the release kinetics. In the third part of this thesis crystallization of n-tetracosane, a saturated hydrocarbon, in nanoporous matrices was studied. n-Tetracosane shows inside AAO membranes the rotator phase sequence: triclinic−RV−RI−RII−liquid. Further, the long axes of the n-tetracosane molecules are oriented normal to the AAO pore axes. In general, n-tetracosane under confinement shows a more complex phase behavior than the polymeric analogue polyethylene. The presented work expands the available strategies for mesoscopic crystal engineering. The methods might be transferred into other areas of interest such as polymorphism screening or preparation of different types of nanowires with customized optoelectronic or ferroelectric properties.

Die vorliegende Arbeit befasst sich mit der Charakterisierung und der Wirkung von Mikroseigerungen auf das Werkstoffverhalten moderner 9% Cr-Stähle. Hierzu wurden drei Werkstoffchargen der Güte MARBN hinsichtlich der Mikrostruktur, des Zeitstandverhaltens, des Verhaltens während einer thermo-physikalischen Schweiß- sowie Wärmebehandlungssimulation auf quantitativer Ebene eingehend untersucht. Mit Hilfe von licht-, rasterelektronen- und transmissionselektronenmikroskopischen Untersuchungsmethoden wurden die Art, Größe, Verteilung und Elementzusammensetzung der Mikroseigerungen einer jeden Charge bestimmt. Eine Prüfung des Zeitstandverhaltens bei 650 °C und unterschiedlichen Spannungen zeigte eine chargenabhängige Zeitstandfestigkeit, welche unterhalb der üblichen Zeitstandfestigkeiten für homogene MARBN Güten liegt. Durch die thermo-physikalische Schweißsimulation konnte nachgewiesen werden, dass die Mikroseigerungen sämtlicher Chargen ab einer Spitzentemperatur von 1.000 °C zu unerwünschtem Deltaferrit umwandeln, dessen Ausprägung ebenfalls eine Chargenabhängigkeit zeigte. Weiterhin wurde der Einfluss normalisierender Wärmebehandlungen auf das mikroseigerungsbehaftete Gefüge mit Hilfe von thermo-physikalischer Simulation untersucht. Es zeigte sich, dass alle drei Chargen zur deutlichen Ausbildung von unerwünschtem Deltaferrit im Bereich der Mikroseigerungen bei üblichen Normalisierungstemperaturen neigen. Das chargenabhängig unterschiedliche Werkstoffverhalten konnte mit den charakterisierten Mikrostrukturen und dem Grad der Gefügeinhomogenität korreliert werden. Aus einer Variation der Normalisierungsbedingungen ging hervor, dass durch eine konventionelle einstufige Wärmebehandlung keine homogene und deltaferritfreie Mikrostruktur erzeugt werden kann. Aus diesem Grund wurde eine dreistufige Wärmebehandlung entwickelt und appliziert, mit dem Ziel einer schrittweisen Auflösung und Verteilung der in den Mikroseigerungen gebundenen Elemente. Die Wirksamkeit der Homogenisierungen in Bezug auf die Mikrostruktur, die Elementverteilung, das Schweißverhalten sowie das Zeitstandverhalten konnte erfolgreich nachgewiesen werden. So zeigte sich eine homogene Mikrostruktur, eine signifikante Reduzierung des Deltaferritanteils bei sämtlichen simulierten Spitzentemperaturen, sowie eine deutliche Verbesserung der Zeitstandfestigkeit aller drei Chargen.

Schwerpunkt dieser Arbeit ist die Untersuchung der Struktur von Materialien und ihrer Entwicklung unter in situ Bedingungen. Dabei werden nanoskopische Strukturmotive in amorphen, ungeordneten und porösen Festkörpern mit Hilfe von Kleinwinkelstreuungstechniken identifiziert und quantifiziert. Es werden drei verschiedene wissenschaftliche Fragestellungen bezüglich drei unterschiedlicher Materialsystemen diskutiert. Erstens wird die Nanostruktur von Dichtefluktuationen in hydriertem amorphen Silizium (a-Si:H) charakterisiert. In den untersuchten a-Si:H Materialien wurden zwei unterschiedliche in die a-Si:H-Matrix eingebettete Phasen identifiziert und anhand ihrer Streuquerschnitte quantifiziert. Diese neuen Ergebnisse beantworten eine seit 20 Jahren ungelöste Fragestellung über das a Si:H Material. Zweitens wird die Adsorption, Kondensation und Desorption von Xenon (Xe) in den Poren einer mesoporösen Silizium (Si) Membran untersucht. Dabei werden Xe-spezifischen Charakterisierungsmethoden eingesetzt. Die neuen Ergebnisse führen zu einem detaillierten Verständnis der Physisorption von Xe in porösem Silizium und zeigen deutliche Unterschiede zwischen Porenfüllungs- und Porenentleerungsmechanismen auf. Zuletzt wird die natürliche Alterung (NA) einer Aluminium-Magnesium-Silizium-Modelllegierung diskutiert. Die Streuexperimente weisen auf das Vorhandensein von Segregationszonen hin und unterstützen die Interpretation dieser Zonen als MgSi-Nanophasen in der Al-Matrix. / The investigation of material structures and their evolution under in situ conditions is the main focus of this work. Thereby, nanostructural motives in amorphous, disordered, and porous solids are identified and quantified using small-angle scattering techniques. Three different scientific questions concerning three different material systems are discussed. First, the nanostructure of density fluctuations in hydrogenated amorphous silicon (a-Si:H) is evaluated and quantified. Second, the adsorption, condensation, and desorption of xenon (Xe) confined in the pores of a mesoporous silicon (Si) membrane is studied in situ using Xe-specific characterization methods. Finally, the natural aging (NA) of an aluminum-magnesium-silicon model alloy (Al-0.6Mg-0.8Si) is discussed.

Die ausWestafrika stammende Ölpalme (Elaeis guineensis Jacq) ist zur populärsten Kulturpflanze in Südostasien geworden. Als Haupterzeugnisse dieser Pflanze gelten die Öle der Früchte und der Fruchtkerne. Die weltweite Nachfrage nach diesen beiden Haupterzeugnissen nimmt sehr rasch zu. Ursache hierfür ist die breite Anwendungspalette dieser Pflanzenöle, wie z.B. Bratöl, ölbasierte Chemikalien und ölbasierte Nahrungsmittel, Kosmetika, Waschmittel, Biobrennstoff usw. Indonesien und Malaysia sind die Hauptproduzenten und Hauptlieferanten solcher Produkte und decken über 85% des weltweiten Bedarfs. Mit Extensivierung der Ölpalmplantagen sehen sich die Erzeugerländer zunehmend mit ernstzunehmenden Umweltprobleme konfrontiert, da nach Erreichen der wirtschaftlichen Lebenspanne (Umtriebszeit) von 25 Jahren große Mengen an festen, biologischen Abfallstoffe bei der Neubegründung der Bestände anfallen. So sollen z.B. im Jahre 2010 laut Vorhersagen mehr als 20 Mill. Kubikmeter Ölpalmen- Holz jährlich anfallen... / Oil palm (Elaeis guineensis Jacq) becomes the most popular crop, especially in Southeast Asia, than its origin,West Africa. World demand of two main products from this crop (e.g. crude palm oil and palm kernel oil) increases very rapidly, due to very wide ranges use of these vegetable oils for industrial purposes, such as fried oil, oleo-chemical and -food, cosmetics, detergent, biofuel and etc. Indonesia and Malaysia are the main producers and supplying more than 85% of world consumption. On the other hand, due to the economic life span of this popular crop (25 years), the producer countries have been facing a serious environmental problems concerning to the solid biowaste handling of oil palm industry, particularly the oil palm trunk after replanting activity. Starting 2010, it is predicted that more than 20 millions cubic meter biomass from oil palm trunk available annually...