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In der organischen Elektronik werden Moleküle mit konjugierten pi-Elektronensystemen als Halbleiter und Lichtemitter eingesetzt. Für die Fabrikation fortschrittlicher elektronischer Bauelemente, wie z. B.organischer Leuchtdioden, werden Materialien mit besonderen optoelektronischen Eigenschaften benötigt.Die Stoffklasse der Arylamine ist für den Transport positiver Ladungen etabliert, da die exozyklischen Stickstoffatome Elektronenlöcher mesomer zu stabilisieren vermögen. Komplementär dazu sind auch Materialien für den Transport negativer Ladungen in der organischen Elektronik unverzichtbar. Zu diesem Zweck sollten borhaltige Verbindungen ideal geeignet sein, da das Element Bor weniger Valenzelektronen als Kohlenstoff besitzt und Arylborane daher im Vergleich zu den entsprechenden Kohlenwasserstoffen eine geringere Elektronendichte aufweisen. Als Halbleitermaterialien sind Arylborane jedoch nicht so weit verbreitet wie Arylamine, da die Instabilität vieler Vertreter gegenüber Luft und Feuchtigkeit sowie der Mangel an effizienten Synthesemethoden ihre Anwendung verzögert haben. Um geeignete organische Elektronenleiter bereitzustellen, ist die Entwicklung stabiler, pi-konjugierter Borane erstrebenswert. Ansatzpunkte für diese Arbeit waren Erkenntnisse aus der vorangegangenen Masterarbeit, sowie Beispiele für hydrolysestabile Arylborane, welche in der jüngeren Vergangenheit von M. Wagner et al. Und S. Yamaguchi et al. veröffentlicht wurden. Im Rahmen der vorliegenden Arbeit gelang die Entwicklung einer modularen Synthesestrategie, die einen vielseitigen Zugang zur Stoffklasse der borhaltigen polyzyklischen aromatischen Kohlenwasserstoffe (PAKs) ermöglicht: Ausgehend von einem gut verfügbaren siliziumhaltigen Startmaterial und diversen, zum Großteil kommerziell erhältlichen, Carbonylverbindungen wurden mehr als zwanzig verschiedene Triarylborane dargestellt. Dabei wurde eine Auswahl spezieller Reaktionstypen nach den jeweiligen Erfordernissen in geeigneter Weise miteinander kombiniert. Zu diesen gehörte die Peterson-Olefinierung zum Aufbau drei- und vierfach substituierter Alkene, die Photozyklisierung der resultierenden Stilben-artigen Verbindungen, eine Ru(II)-katalysierte Reaktion zur Benzanellierung und der Silizium/Bor Austausch mittels BBr3. An wichtigen Zwischenprodukten wurden Reaktivitätsstudien durchgeführt, um die Anwendungsmöglichkeiten und Einschränkungen dieser Synthesestrategie zu ergründen. Um die Stabilität der Produkte gegenüber Luft und Feuchtigkeit zu gewährleisten, wurden die reaktiven Borzentren in bewährter Weise durch Einführung eines sterisch anspruchsvollen Mesitylsubstituenten kinetisch abgeschirmt. Die überwiegende Zahl der synthetisierten borhaltigen PAKs erwies sich als absolut unempfindlich gegenüber Wasser und konnte mit den gängigen Methoden der organischen Chemie (z. B. Säulenchromatographie an Kieselgel) gereinigt werden. Als Alternative zur sterischen Abschirmung wurde der Einbau des Boratoms in ein starres Molekülgerüst an einem Ausführungsbeispiel verwirklicht. Diese zweite Möglichkeit der Stabilisierung stellte sich in Bezug auf die Eigenschaften des Produkts als vergleichbar heraus, erforderte aber einen größeren synthetischen Aufwand und lieferte eine geringere Ausbeute über die gesamte Reaktionssequenz. Die in dieser Arbeit dargestellten borhaltigen PAKs wurden mittels Röntgenkristallographie umfassend strukturell charakterisiert. Die intensiv genutzten Methoden Cyclovoltammetrie, UV/vis- und Fluoreszenzspektroskopie gewährten zusätzlich einen detaillierten Einblick in ihre elektronischen Strukturen. Die Synthese und systematische Variation der Moleküle führten zu neuen Erkenntnissen über grundlegende Struktur-Eigenschafts-Beziehungen. Insbesondere zeigten diese Vergleiche, dass in ladungsneutralen Triarylboranen keine Delokalisation der pi-Elektronen über das leere p-Orbital eines Boratoms stattfindet. Von entscheidender Bedeutung für die elektronische Struktur borhaltiger PAKs ist das Gerüst aus sp2-hybridisierten Kohlenstoffatomen: Wenn mindestens zwei der Arylsubstituenten am Boratom zu einem gemeinsamen Gefüge verbrückt sind, zeigen diese Verbindungen elektronische Übergänge im sichtbaren Bereich des elektromagnetischen Spektrums und in den meisten Fällen auch eine intensive Fluoreszenz. Des Weiteren besitzen diese borhaltigen PAKs eine hohe Elektronenaffinität und lassen sich elektrochemisch reversibel reduzieren. Damit erfüllen sie bedeutende Kriterien für eine mögliche Anwendung als Elektronenleiter. Von den Molekülen mit ausgedehntem pi-Elektronensystem ließen sich manche zusätzlich reversibel oxidieren und zeichnen sich daher durch eine außergewöhnlich hohe elektrochemische Stabilität aus. An Arylboranen, deren Farbe sich durch externe Stimuli verändern lässt, wurden grundlegende Untersuchungen im Kontext der molekularen Sensorik durchgeführt. Einige der synthetisierten Verbindungen ändern ihr Absorptions- und Emissionsspektrum bei Kontakt mit Fluorid-Ionen, bei Oxidation integrierter Schwefelatome durch ein Carbonsäureperoxid, bei elektrochemischer Reduktion oder in Abhängigkeit der Polarität ihrer Umgebung. Die Ergebnisse dieser Arbeit wurden in vier Fachartikeln beschrieben und veröffentlicht (siehe Anhang). Sie können zu einem besseren Verständnis der elektronischen Eigenschaften borhaltiger PAKs beitragen und die Entwicklung neuer Halbleitermaterialien auf der Basis dieser Stoffklasse erleichtern.
Ausgangspunkt der vorliegenden Arbeit ist die Frage, inwieweit Lessing in seiner Konzeption von Metaphern durch andere Autoren beeinflusst wurde. Ziel der Abhandlung ist es, darzulegen, dass Lessing bei dem mecklenburgischen Philologen Michael Conrad Curtius Anregungen für den Aufbau und den Gebrauch von Gleichnissen und Metaphern gewann. Zunächst referiere ich den Inhalt des hierfür relevanten Werks von Curtius, der "Abhandlung von den Gleichnissen und Metaphern und deren poetischem Gebrauche". Anschließend folgt ein historischer Ausblick auf Lessings Rezeption von Curtius' Schriften. Schließlich wende ich die Curtius'schen Theorien und Schemata auf Lessings Fabeln "Der Naturalist" und "Die Pfauen und die Krähe" an.
Background: Electrical stimulation (ES) has been successfully used to treat bone defects clinically. Recently, both cellular and molecular approaches have demonstrated that ES can change cell behavior such as migration, proliferation and differentiation.
Methods: In the present study we exposed rat bone marrow- (BM-) and adipose tissue- (AT-) derived mesenchymal stem cells (MSCs) to direct current electrical stimulation (DC ES) and assessed temporal changes in osteogenic differentiation. We applied 100 mV/mm of DC ES for 1 h per day for three, seven and 14 days to cells cultivated in osteogenic differentiation medium and assessed viability and calcium deposition at the different time points. In addition, expression of osteogenic genes, Runx2, Osteopontin, and Col1A2 was assessed in BM- and AT-derived MSCs at the different time points.
Results: Results showed that ES changed osteogenic gene expression patterns in both BM- and AT-MSCs, and these changes differed between the two groups. In BM-MSCs, ES caused a significant increase in mRNA levels of Runx2, Osteopontin and Col1A2 at day 7, while in AT-MSCs, the increase in Runx2 and Osteopontin expression were observed after 14 days of ES.
Discussion: This study shows that rat bone marrow- and adipose tissue-derived stem cells react differently to electrical stimuli, an observation that could be important for application of electrical stimulation in tissue engineering.
Cleaning an ion beam from unwanted fractions is crucial for intense ion beams. This thesis will explore separation methods using a collimation channel, electric and magnetic dipoles and a velocity selector for low intensity beams on an experimental basis. In addition, statistical data of degassing events during the commissioning of a pentode extraction system for beam energies from 20 - 120keV will be presented.
Background/objectives: Obesity is independently associated with left ventricular (LV) diastolic dysfunction and altered cardiac morphology. Morbidity and mortality in patients with diastolic dysfunction are similar to values observed in patients with systolic heart failure. We hypothesized that dysfunctional cardiac responses in people with obesity are reversible after weight loss. Thus, we studied the effect of dietary weight reduction on LV diastolic function as well as on cardiac structure using transthoracic echocardiography and tissue Doppler imaging (TDI).
Subjects/methods: Thirty-two subjects with obesity underwent a 12-week low-calorie fasting phase of a formula diet. Echocardiographic tissue Doppler indices of diastolic function and measurements of cardiac size were obtained prior to and after the fasting phase.
Results: A 12-week diet significantly reduced body mass index from 40.3 ± 6.6 kg/m 2 to 33.2 ± 6.1 kg/m 2 ( p < 0.01). Weight loss was associated with a significant reduction in blood pressure and heart rate. Echocardiography revealed diastolic dysfunction in subjects with obesity, which was improved by dieting. After weight loss, trans-mitral Doppler echocardiography showed a significant reduction in A-wave velocity, from 65.8 ± 19.2 cm/s to 57.0 ± 16.8 cm/s, and an increase in E/A ratio from 1.2 ± 0.4 to 1.4 ± 0.5 ( p < 0.01). TDI displayed a significantly lower a'-wave velocity (10.3 ± 2.3 cm/s and 8.9 ± 1.7 cm/s; p < 0.01). Left atrial and LV dimensions were normal and remained unchanged after weight loss.
Conclusion: Obesity is associated with diastolic dysfunction. A 12-week low-calorie diet with successful weight loss can reduce blood pressure and heart rate and partially normalize diastolic dysfunction.
This thesis aimed at identifying and understanding the interplay of charge and lattice degrees of freedom at metal-insulator transitions that are driven by strong electron correlations, i.e., Mott and charge-order metal-insulator transitions. To this end, measurements of the thermal expansion were performed, which have proven to be particularly suited to deliver insight into the role of lattice degrees of freedom in strongly correlated electron systems. Prime examples of such systems are the herein studied organic charge-transfer salts which stand out by a high tunability of the interaction strength.
The central topic of this thesis was the investigation of the universal behavior of the pressure-induced finite-temperature Mott critical endpoint in the organic charge-transfer salt kappa-(BEDT-TTF)2Cu[N(CN)2]Cl. In the present work, it was proven experimentally that lattice effects play a crucial role for the universal behavior, in contrast to the assumption made in previous works.
We present an implementation of an interpreter LRPi for the call-by-need calculus LRP, based on a variant of Sestoft's abstract machine Mark 1, extended with an eager garbage collector. It is used as a tool for exact space usage analyses as a support for our investigations into space improvements of call-by-need calculi.
Frühe mathematische Bildung – Ziele und Gelingensbedingungen für den Elementar- und Primarbereich
(2017)
Im Rahmen der Schriftenreihe "Wissenschaftliche Untersuchungen zur Arbeit der Stiftung 'Haus der kleinen Forscher'" werden regelmäßig wissenschaftliche Beiträge von renommierten Expertinnen und Experten aus dem Bereich der frühen Bildung veröffentlicht. Diese Schriftenreihe dient einem fachlichen Dialog zwischen Stiftung, Wissenschaft und Praxis, mit dem Ziel, allen Kitas, Horten und Grundschulen in Deutschland fundierte Unterstützung für ihren frühkindlichen Bildungsauftrag zu geben.
Der vorliegende achte Band der Reihe mit einem Geleitwort von Kristina Reiss stellt die Ziele und Gelingensbedingungen mathematischer Bildung im Elementar- und Primarbereich in den Fokus.
Christiane Benz, Meike Grüßing, Jens Holger Lorenz, Christoph Selter und Bernd Wollring spezifizieren in ihrer Expertise pädagogisch-inhaltliche Zieldimensionen mathematischer Bildung im Kita- und Grundschulalter. Neben einer theoretischen Fundierung verschiedener Zielbereiche werden Instrumente für deren Messung aufgeführt. Des Weiteren erörtern die Autorinnen und Autoren Gelingensbedingungen für eine effektive und wirkungsvolle frühe mathematische Bildung in der Praxis. Sie geben zudem Empfehlungen für die Weiterentwicklung der Stiftungsangebote und die wissenschaftliche Begleitung der Stiftungsarbeit im Bereich Mathematik.
Das Schlusskapitel des Bandes beschreibt die Umsetzung dieser fachlichen Empfehlungen in den inhaltlichen Angeboten der Stiftung "Haus der kleinen Forscher".
The lumbodorsal fascia (LF) has been proposed to represent a possible source of idiopathic low back pain. In fact, histological studies have demonstrated the presence of nociceptive free nerve endings within the LF, which, furthermore, appear to exhibit morphological changes in patients with chronic low back pain. However, it is unclear how these characteristics relate to the aetiology of the pain. In vivo elicitation of back pain via experimental stimulation of the LF suggests that dorsal horn neurons react by increasing their excitability. Such sensitization of fascia-related dorsal horn neurons, in turn, could be related to microinjuries and/or inflammation in the LF. Despite available data point towards a significant role of the LF in low back pain, further studies are needed to better understand the involved neurophysiological dynamics.
Broad AOX expression in a genetically tractable mouse model does not disturb normal physiology
(2017)
Plants and many lower organisms, but not mammals, express alternative oxidases (AOXs) that branch the mitochondrial respiratory chain, transferring electrons directly from ubiquinol to oxygen without proton pumping. Thus, they maintain electron flow under conditions when the classical respiratory chain is impaired, limiting excess production of oxygen radicals and supporting redox and metabolic homeostasis. AOX from Ciona intestinalis has been used to study and mitigate mitochondrial impairments in mammalian cell lines, Drosophila disease models and, most recently, in the mouse, where multiple lentivector-AOX transgenes conferred substantial expression in specific tissues. Here, we describe a genetically tractable mouse model in which Ciona AOX has been targeted to the Rosa26 locus for ubiquitous expression. The AOXRosa26 mouse exhibited only subtle phenotypic effects on respiratory complex formation, oxygen consumption or the global metabolome, and showed an essentially normal physiology. AOX conferred robust resistance to inhibitors of the respiratory chain in organello; moreover, animals exposed to a systemically applied LD50 dose of cyanide did not succumb. The AOXRosa26 mouse is a useful tool to investigate respiratory control mechanisms and to decipher mitochondrial disease aetiology in vivo.
ʿAzīmabādīs Erläuterung des Taǧdīd-Hadithes als Beispiel eines religiösen Autorisierungsdiskurses
(2017)
This paper discusses the syntax of relative clauses in European Portuguese (EP) by focussing on the status of the relativizer que in restrictive and appositive relative clauses. We propose a unified account of que in terms of a D-element and discuss the syntactic implications of this assumption for an adequate analysis of relative clauses in EP. We assume that relative que has properties of demonstrative and interrogative determiners. In restrictive object and subject relative clauses, que occurs as a transitive determiner [DP que [NP e]], which selects for a nominal complement, whereas in prepositional and appositive relative clauses, [DP que] is an intransitive determiner parallel to an e-type pronoun. We discuss the position of restrictive relative clauses in the DP containing the modified noun, and propose that they are merged pre-nominally, in the same fashion as demonstratives.
The disruption of coupling between brain areas has been suggested as the mechanism underlying loss of consciousness in anesthesia. This hypothesis has been tested previously by measuring the information transfer between brain areas, and by taking reduced information transfer as a proxy for decoupling. Yet, information transfer is a function of the amount of information available in the information source—such that transfer decreases even for unchanged coupling when less source information is available. Therefore, we reconsidered past interpretations of reduced information transfer as a sign of decoupling, and asked whether impaired local information processing leads to a loss of information transfer. An important prediction of this alternative hypothesis is that changes in locally available information (signal entropy) should be at least as pronounced as changes in information transfer. We tested this prediction by recording local field potentials in two ferrets after administration of isoflurane in concentrations of 0.0%, 0.5%, and 1.0%. We found strong decreases in the source entropy under isoflurane in area V1 and the prefrontal cortex (PFC)—as predicted by our alternative hypothesis. The decrease in source entropy was stronger in PFC compared to V1. Information transfer between V1 and PFC was reduced bidirectionally, but with a stronger decrease from PFC to V1. This links the stronger decrease in information transfer to the stronger decrease in source entropy—suggesting reduced source entropy reduces information transfer. This conclusion fits the observation that the synaptic targets of isoflurane are located in local cortical circuits rather than on the synapses formed by interareal axonal projections. Thus, changes in information transfer under isoflurane seem to be a consequence of changes in local processing more than of decoupling between brain areas. We suggest that source entropy changes must be considered whenever interpreting changes in information transfer as decoupling.
Aesthetic perception and judgement are not merely cognitive processes, but also involve feelings. Therefore, the empirical study of these experiences requires conceptualization and measurement of aesthetic emotions. Despite the long-standing interest in such emotions, we still lack an assessment tool to capture the broad range of emotions that occur in response to the perceived aesthetic appeal of stimuli. Elicitors of aesthetic emotions are not limited to the arts in the strict sense, but extend to design, built environments, and nature. In this article, we describe the development of a questionnaire that is applicable across many of these domains: the Aesthetic Emotions Scale (Aesthemos). Drawing on theoretical accounts of aesthetic emotions and an extensive review of extant measures of aesthetic emotions within specific domains such as music, literature, film, painting, advertisements, design, and architecture, we propose a framework for studying aesthetic emotions. The Aesthemos, which is based on this framework, contains 21 subscales with two items each, that are designed to assess the emotional signature of responses to stimuli’s perceived aesthetic appeal in a highly differentiated manner. These scales cover prototypical aesthetic emotions (e.g., the feeling of beauty, being moved, fascination, and awe), epistemic emotions (e.g., interest and insight), and emotions indicative of amusement (humor and joy). In addition, the Aesthemos subscales capture both the activating (energy and vitality) and the calming (relaxation) effects of aesthetic experiences, as well as negative emotions that may contribute to aesthetic displeasure (e.g., the feeling of ugliness, boredom, and confusion).