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Die vorliegende Arbeit trägt den Titel: Intellektuellen-Rolle in Günter Grass Werken : „Die Plebejer proben den Aufstand“(1966), „Örtlich betäubt“(1969), „Aus dem Tagebuch einer Schnecke“(1972), und „Ein weites Feld“(1995).
Das erste Kapitel befasst sich insgesamt mit drei Haupttiteln
II. Der Intellektuelle
II.1 Das allgemeine Umfeld
In diesem Teil der Dissertation sollen Aussagen getroffen werden, die auf folgende und weitere Fragen eine Antwort geben: Was ist ein Intellektueller? Wie kam der Begriff zustande? Gibt es Unterschiede zwischen den Intellektuellen und wie werden sie eingeteilt?
II.2 Das deutsche Umfeld
Die Behandlung des Nazisystems und dessen historische Hintergründe vermittelt bedeutsame Lehren. Aber wozu braucht man diese Lehren? Gibt es Spuren von Nationalsozialismus heutzutage? Wo waren die Intellektuellen bei der Bildung des Nationalsozialismus? Ist der Nationalsozialismus erst mit Hitler aufgetaucht? Wenn zuvor, in welcher Phase hat er sich im Bewusstsein der Deutschen verankert? Ob theoretische bzw. geistige Tendenzen dazu beigetragen haben?
II.3 Das Bild von Grass als Intellektueller
II.3.1 Positionierung
Eine Hauptthese für Grass intellektuelle Positionierung wird durch die Verbindung zwischen Grass’ Grundkonzeption der gesellschaftspolitischen Intellektualität und der Gruppe 47 ermittelt. Dann bezweckt die Behandlung von Grass Bild nach Erscheinen seines autobiographischen Werks: „Beim Häuten der Zwiebel“ (2006), dass seine Intellektualität nicht nur aus dem positiven, sondern auch aus dem negativen Profil beleuchtet wird.
Aus der Darstellung zahlreicher Ansichten von Günter Grass werden fünf thematische Kernpunkte als Konzepte behandelt. Unter jedem Konzept sollen spezifische Vorschläge zur gesellschaftlichen Positionierung aufgezeigt werden.
II.3.2 Grass’ politische Merkmale
Es handelt sich hier um die intellektuellen Charaktereigenschaften. Dadurch kommen manche Fragen zu Wort: Hat Günter Grass gesellschaftliche Aktivitäten? Hat er die Voraussetzungen dafür? Wie ist der Umfang seiner Aktivitäten? Hat die Gruppe 47 Einfluss auf Grass intellektuelle Merkmale? Steht bei Grass eine Methode der gesellschaftspolitischen Arbeit zur Verfügung?
Dann wird die politische Sprache von Günter Grass und ihre Wirkung auf den Rezipienten untersucht. Danach wird nach Grass’ Auffassung von der Revision gefragt und ob sie mit seiner Auffassung der Aufklärung zusammenpasst. Darauf wird die Funktion der Revision in seinem literarischen Werk und in seiner gesellschaftspolitischen Aktivität gezeigt.
Abschließend werden die Argumente seiner Intellektualität untersucht:
Wie hat Grass’ gesellschaftspolitische Aktivität den konkreten politischen Rahmen berücksichtigt? Um diese Frage zu beantworten, muss der Zusammenhang zwischen Politik und Moral verdeutlicht werden.
III. Historischer Kontext und Inhalt der Werke
Unter diesem Titel wird erstens der historische Zusammenhang der untersuchten Werke skizziert. Dann werden meistens durch Argumente aus jedem Werk selbst nicht nur der Kern des Werkes und sein Handlungsverlauf, sondern auch die dafür angewandte Methode dargestellt.
IV. Bezug der untersuchten Werke zu konkreten gesellschaftspolitischen Fragen
IV.1 Interaktionswege des Intellektuellen mit der Gesellschaft, vor allem beim Wandel gesellschaftspolitischer Prozesse
Zentralkonzepte des ersten Werkes sind: Vermittlung, Engagement, Solidarität und die Aktualität als Maßstab. Diese werden durch zwei Konzepte des zweiten Werkes: Appell an Generationen beim Wechsel und Zusammenhaltsprinzip an Revision gebunden, sowie durch die Behandlung vom Prozess der Meinungsbildung im vierten Werk ausgearbeitet.
IV.2 Thematische Aspekte zur Vermeidung eines Naziregimes
Aus den thematischen Perspektiven der drei letzten Werke geht eine bunte Sammlung intellektueller Konzepte aus, die zur Bekämpfung von Nazivorsprünge verwendet werden können.
V. Pädagogische Strategien der untersuchten Werke
Die pädagogischen Aspekte der untersuchten Werke sollen intellektuelle Werte vermitteln, die einen bedeutenden Beitrag zur Lösung gesellschaftspolitischer Probleme und Konflikte leisten.
VI. Entwicklung der literarischen und gesellschaftspolitischen Vision
Hier wird die Entwicklungslinie der gesellschaftspolitischen Vision in den untersuchten Werken verfolgt.
VII. Zur Rezeption der vier Werke
Durch die Auseinandersetzung mit der negativen Kritik wird angestrebt, ihre Subjektivität darzulegen, damit der gesellschaftspolitische Wert der vier Werke enthüllt wird.
Although it has become common practice to build applications based on the reuse of existing components or services, technical complexity and semantic challenges constitute barriers to ensuring a successful and wide reuse of components and services. In the geospatial application domain, the barriers are self-evident due to heterogeneous geographic data, a lack of interoperability and complex analysis processes.
Constructing workflows manually and discovering proper services and data that match user intents and preferences is difficult and time-consuming especially for users who are not trained in software development. Furthermore, considering the multi-objective nature of environmental modeling for the assessment of climate change impacts and the various types of geospatial data (e.g., formats, scales, and georeferencing systems) increases the complexity challenges.
Automatic service composition approaches that provide semantics-based assistance in the process of workflow design have proven to be a solution to overcome these challenges and have become a frequent demand especially by end users who are not IT experts. In this light, the major contributions of this thesis are:
(i) Simplification of service reuse and workflow design of applications for climate impact analysis by following the eXtreme Model-Driven Development (XMDD) paradigm.
(ii) Design of a semantic domain model for climate impact analysis applications that comprises specifically designed services, ontologies that provide domain-specific vocabulary for referring to types and services, and the input/output annotation of the services using the terms defined in the ontologies.
(iii) Application of a constraint-driven method for the automatic composition of workflows for analyzing the impacts of sea-level rise. The application scenario demonstrates the impact of domain modeling decisions on the results and the performance of the synthesis algorithm.
תקציר
מצוות הפריון הינה אחת מן המצוות החשובות ביהדות ומגדירה במובנים רבים את מהות קיומו של האדם היהודי הדתי. זוגות דתיים אשר סובלים מבעיית פריון נקרעים לא פעם בין מחוייבותם הדתית והלחץ החברתי בקהילתם לבין אי יכולתם להביא ילדים לעולם בדרך טבעית. החל מאמצע המאה ה 20- הפכו טכנולוגיות פריון רפואיות לנגישות לציבור הרחב בישראל ובעולם והובילו למהפכה חברתית אשר אפשרה לזוגות חשוכי ילדים להגשים את חלומם בפעם הראשונה ולהפוך להורים. פריצת דרך רפואית זו לא נעלמה מעיני הציבור הדתי על זרמיו השונים וגרמה לטלטלה בתפיסת עולמם של מנהיגיהם, אשר נדרשו לתת מענה הלכתי הולם המאזן בין רווחת קהילותיהם לבין שמירה על ערכי ומצוות הדת היהודית. על רקע תמורות אלו התפתח שיח הלכתי ואקדמי חשוב ומעניין באשר למקומה של טכנולוגיה מודרנית בחברה המתנהלת על פי קודים מסורתיים. עם זאת, הדיאלוג החי המתקיים בין מנהיגי היהדות לבין קהילותיהם, אשר מתועד כאוסף שאלות ותשובות (שו"ת) לבעיות הלכתיות אקטואליות בתחום הפריון, לא נחקר דיו.
עבודתנו עוסקת במחקר ספרות השו"ת ובגישת פוסקי ההלכה להסתייעות בטכנולוגיית ההזרעה המלאכותית ובטיפולי פוריות חדשניים נוספים שהתפתחו בעקבותיה כגון הפריה חוץ גופית, פונדקאות ותרומת ביציות. העבודה סוקרת את התגבשות ועיצוב ההלכה בשאלה זו, כפי שעולה מספרות השו"ת החל מתקופת הראשונים (המאות ה 11- עד ה- 16 ) ועד לפוסקים מתקופת האחרונים (המאה ה- 16 ואילך), ומתמקדת בעיקר בתקופה המודרנית של המאה האחרונה. במרכז העבודה יעמדו מעמדם ההלכתי של האם והוולד בעקבות שימוש בהזרעה והפריה מלאכותית וכן השלכותיהן ההלכתיות של השימוש הרפואי בזרע.
תרומתו של מחקר זה הינה בהצגת וניתוח התמודדות הפוסקים עם העימות הערכי וההלכתי שמעוררות תמורות במבנה המשפחה ובדפוסי הורות מסורתיים כתוצאה משימוש הולך וגובר בטכנולוגיות פריון מתקדמות בחברה המודרנית. יתר על כן, מחקר זה מרחיב את הדיון ההלכתי אל מעבר לעמדות הפוסקים ביהדות האורתודוקסית, הנצמדים לעקרונות ההלכה ההיסטורית, ומציג לראשונה אף את קשת הדעות של רבנים המשתייכים לזרמי היהדות המתקדמת והקונסרבטיבית, הדוגלים בפיתוח ההלכה והתאמתה למציאות החיים המשתנה. כך, מעניקה עבודת מחקר זו תמונה שלמה ומקיפה יותר באשר להתמודדות הרבנים עם שאלת ההזרעה המלאכותית ומציגה את רב גוניותה של ההלכה כפי שמשתקפת בזרמי היהדות השונים בישראל ובתפוצות.
העבודה מחולקת לשישה חלקים אשר יפורטו בקצרה להלן.
חלק ראשון - מבוא לשאלת ההזרעה המלאכותית בספרות השו"ת
חלק זה מהווה מבוא והקדמה תיאורטית ומחקרית לשאלת ההזרעה המלאכותית ומטרתו לצייד את הקורא ברקע ההיסטורי ובכלים המחקריים הדרושים להמשך העבודה. הפרק הראשון סוקר מצוות דתיות והשקפות תרבותיות בנוגע לילודה בחברה היהודית ואילו הפרק השני מניח יסודות מתודולוגיים והיסטוריים הנחוצים לחקר שאלת ההזרעה המלאכותית בספרות השו"ת.
פרק ראשון - מצוות דתיות והשקפות תרבותיות בנוגע לילודה בחברה היהודית
פרק זה מציג את המשנה האידיאולוגית העומדת בבסיס ההצדקה ההלכתית להתרתם של טיפולי הפוריות. הפרק דן בחשיבות מצוות הפריון כפי שעולה ממקורות הלכתיים קדומים וברקע ההיסטורי והתרבותי למרכזיותה של מצווה זו ומצוות נלוות לה בדת היהודית. הפרק מדגים כיצד עיצבה חשיבות המצווה את דפוס המשפחה היהודית לאורך ההיסטוריה ועד לימינו ומסתיים בדיון קצר בשאלות רפואיות מוסריות העולות מהנגשת טכנולוגיות פריון מתקדמות במדינת ישראל המודרנית.
פרק שני - יסודות מתודולוגיים והיסטוריים בחקר שאלת ההזרעה המלאכותית בספרות השו"ת
בפרק זה מוצגים תחילה מטרות ושיטות המחקר אשר נבחרו לשם ניתוח הפסיקה בשאלת ההזרעה המלאכותית. מכיוון שהעבודה עוסקת בשאלה רפואית חדשנית והשפעתה על העולם הדתי, יערך מחקר זה תוך שימוש בניתוח רב מימדי המשלב מספר שיטות מחקר ובראשן השיטה הדוגמטית-היסטורית, כמו גם בניתוח ביקורתי של שיקולי המדיניות העומדים בבסיס שיקולי הפוסקים לפי אסוכלת הריאליזים ההלכתי. לאחר מכן נסקרים ונידונים המקורות ההיסטוריים העיקריים אשר עוסקים בהתעברות על טבעית באמבט או באמצעות שכיבה על סדינים והעומדים בבסיס הכרעות הפוסקים בהשלכות הזרעה מלאכותית על מעמדם ההלכתי של האישה והילוד.
חלק שני- ספרות השו"ת האורתודוקסית בשאלת הזרעה מלאכותית מן הבעל
חלקו שני של המחקר עוסק בניתוח ספרות השו"ת האורתודוקסית בשאלת הזרעה מלאכותית מן הבעל ובוחן את התפתחותו הרעיונית של איסור השחתת זרע ואת עמדות הפוסקים בשאלת הזרעה מלאכותית מן הבעל כפי שנידונה בספרות השו"ת.
פרק ראשון - התפתחותו הרעיונית של איסור השחתת זרע
בפרק זה נסקרים מקורותיו ההיסטוריים של האיסור להשחתת זרע. איסור זה נושק לכל תחומי חייו של הזוג הדתי ובעיקר לתחום המיניות והפריון ובעל השפעה מהותית על מגבלות הצניעות שהוחלו בעקבותיו על המיניות הגברית. קיים ויכוח בין החוקרים האם נובע האיסור מן המקורות העתיקים כגון התלמוד או לחילופין התעצם בעקבות החמרות הרבנים. מחקרינו מציע כי האפשרות השניה היא הסבירה יותר. חכמי התלמוד מפגינים גישה מקלה כלפי האיסור אך מביעים סלידה מהוצאת זרע לבטלה מתוך חשיבה חסידית או אמונה כי עיסוק בעינוג מיני עצמי עלול להסיט את האדם מקיום מצוות הפריון. לעומת זאת, בספרות הקבלה ובמיוחד בזוהר ניכרת החמרה במימדי האיסור החודרת מאוחר יותר אל עולם ההלכה.
פרק שני - דיון בהזרעה מן הבעל בספרות השו"ת
הפרק דן בפסיקותיהם של רבנים בולטים בזרם האורתודוקסי בשאלת ההזרעה מן הבעל. בספרות השו"ת האורתודוקסית ניכרת השפעתו של איסור הוצאת זרע לבטלה על שיקולי הפוסקים באם להתיר את הטיפול בהזרעה מלאכותית מן הבעל. פוסקים מקלים כגון הרבנים פיינשטיין, נבנצל ויוסף מייחסים משקל רב יותר לחשיבות מצוות הפריון ומצמצמים בשל כך את תחולת האיסור. לעומתם, פוסקים מחמירים ובראשם הרבנים טננבוים, קוק, עוזיאל, הדאיה ולדנברג מתנגדים לטיפולי פוריות מחשש השחתת זרע ובשל השלכותיה הרוחניות של העבירה על האיסור. שאלה מהותית נוספת בשיח ההלכתי בה נחלקו הרבנים הינה באשר לאפשרות קיומה של מצוות הפריה והרביה באמצעות הריון שהושג בסיוע רפואי. פוסקים מדור האחרונים, כגון הרבנים טננבוים, סגל ואזולאי (החיד"א), ובעקבותיהם פוסקים בולטים במאה ה- 20 וה- 21 כמו הרבנים עוזיאל, הדאיה, ולדנברג וקניבסקי סברו כי ניתן לקיים את המצווה באופן טבעי בלבד. לעומת זאת, הרבנים נבנצל, יוסף, וינברג ואוירבך ייחסו חשיבות רבה יותר לכוונת העושה ולתוצאה המיוחלת של ההריון אשר מגשימה לדעתם את הרציונל העומד בבסיס מצוות הפרייה הרבייה ובמצוות ישוב העולם.
שאלה נוספת המתעוררת בעניין הזרעה מן הבעל ונידונה בפרק זה עוסקת בבעיית העקרות ההלכתית. התעקשות הרבנים לשמור על הלכות הנידה במתכונתן המסורתית חושפת נשים דתיות לאי ודאות באשר לטהרתן ומכפיפה את חיי המין והפריון של משפחות שלמות למרות הסמכות הרבנית.
חלק שלישי- ספרות השו"ת האורתודוקסית בשאלת הזרעה מלאכותית מתורם
חלקו השלישי של המחקר עוסק בדיון ההלכתי האורתודוקסי בשאלת ההזרעה המלאכותית מתורם יהודי או נוכרי לאישה נשואה. מרבית הפוסקים הסתייגו מתרומת זרע לאישה נשואה מתורם יהודי כמו גם מנוכרי משיקולים הלכתיים ואידיאולוגיים.
פרק ראשון - שאלת ההזרעה המלאכותית מתורם יהודי
תרומת זרע מתורם יהודי זר מעלה חששות הלכתיים רבים לגבי מעמדה ההלכתי של האישה כגון ניאוף וקיום מצוות הייבום והחליצה. כמו כן הועלו חששות לגבי יחוסו וכשרותו ההלכתית של הקטין כגון חשש ממזרות, גילוי עריות בין ילדי התורם, פגיעה במעמד הכהונה ובעיות בתחום המעמד האישי בשל אי ודאות לגבי זהות התורם. בנוסף, משליכה הכרעה בשאלות אלה על זכאות הקטין לזכויות סוציאליות המגיעות לו מאביו, כגון הזכות למזונות ולירושה. פסיקת ההלכה במאה האחרונה אימצה את עמדתו של הרב פיינשטיין, לפיה רק הריון הנובע ממגע מיני ישיר בין אישה נשואה לגבר זר, בניגוד להזרעה מלאכותית, יכול לפגוע במעמד האישה והילוד. עם זאת, פוסקים רבים אסרו לבצע הזרעה מלאכותית מגבר יהודי מטעמי זהירות, בגין חששות אלו.
פרק שני - הזרעה מלאכותית מתורם לא יהודי לאישה נשואה
על אף שבמקרה של תרומת זרע מנוכרי נעדר הילוד יחוס לאביו הנוכרי וכשרותו נקבעת על פי מעמד האם בלבד, מסתייגים פוסקים רבים מן הפעולה. הפוסקים מונים טיעונים רבים לאיסור תרומת זרע מגבר נוכרי וביניהם חילול השם, פגיעה בביצוע מנהג הייבום והחליצה, ספקות לגבי זכויות הירושה, עידוד ההפקרות המינית ופגיעה ביציבות התא המשפחתי המסורתי. בנוסף חוששים הם מבלבול לגבי זהות אבי הילוד ופגיעה במעמד הכהונה. במהלך המאה ה- 20 ניכרת מגמה בקרב פוסקים העוסקים בקבלה לייחוס תכונות שליליות לזרע נוכרי, אשר עוברות לילוד ובאופן זה פוגעות בקדושת העם היהודי. מעבר לשאלות ההלכתיות מועלים בפרק זה קשיים אתיים אשר מעוררת תרומת זרע אנונימית, המונעת מן הילוד לברר את שורשיו הביולוגיים.
חלק רביעי- יחס הפסיקה האורתודוקסית לשינויים במבנה המשפחה המסורתית
בעקבות שימוש בטכנולוגיות פריון חלק זה מנתח את יחס הפסיקה האורתודוקסית לשינויים במבנה המשפחה המסורתית בעקבות שימוש בטכנולוגיות פריון ומורכב משלושה פרקים: הזרעה מלאכותית לאישה פנויה, הפריה חוץ גופית והקמת משפחה אלטרנטיבית בפרספקטיבה הלכתית אורתודוקסית.
פרק ראשון - הזרעה מלאכותית לאישה פנויה
המוסכמה ההלכתית הינה כי ילדה של אישה פנויה לא ייחשב לממזר, אפילו אם אביו הביולוגי הוא יהודי. למרות זאת אסרו פוסקים מסויימים על הזרעה מלאכותית במקרה זה בגין חששות לייחוס הילוד, גילוי עריות וגזילת ירושת שאר האחים. חלק מן הפוסקים קוראים לאסור הזרעה מלאכותית לאישה פנויה בשם טובת הילד ולא מסיבות הלכתיות. אפשרות נוספת אשר השלכותיה ההלכתיות נידונות בפרק זה הינה ביצוע הזרעה מלאכותית באישה רווקה או אלמנה באמצעות שימוש בזרעו של אדם שנפטר. חשוב לציין כי השימוש בטכנולוגיה זו שנוי במחלוקת בקרב הרבנים בגין החשיבות אותה מייחסת היהדות לערך כבוד המת.
פרק שני - הפריה חוץ גופית
הפריית מבחנה יכולה להתבצע בין בני זוג נשואים בסיוע או ללא היזקקות לתרומת ביצית או זרע. פוסקים אשר התירו את השימוש בטכנולוגיה זו הביעו את חששותיהם בנוגע להשלכותיה ההלכתיות של הפריה החוץ גופית בשל הקושי לפקח על התהליך, הנעשה מחוץ לגוף האדם. מתנגדי הפריית המבחנה סברו כי היא מתערבת במלאכת הבריאה האלוהית ועשויה לדרדר את האנושות מבחינה מוסרית לתכנון ולשיבוט בני אדם.
הפריה חוץ גופית מעוררות שאלות הלכתיות חדשניות ובראשן שאלת הגדרת האמהות, כגון במקרי פונדקאות ותרומת ביציות, מהן הסתייגו מרבית פוסקי הדור במאה ה 20- . הקביעה שאומצה בשיח ההלכתי העכשווי גורסת כי אמו של התינוק תהיה האישה שילדה אותו, גם אם נולד מתרומת ביצית. הכרעה זו מובלעת ברציונל החוקים המסדירים את הפונדקאות במדינת ישראל ואשר מטילים מגבלות הלכתיות על בחירת הפונדקאית לשם מניעת חשש ממזרות או שאלה לגבי יהדותו של הילוד.
פרק שלישי - הקמת משפחה אלטרנטיבית בפרספקטיבה הלכתית אורתודוקסית
קיימת בעיה הלכתית מהותית במיסוד הקשר החד-מיני ביהדות האורתודוקסית. ספרות השו"ת האורתודוקסית אינה עוסקת במפורש בשאלת השימוש בהזרעה מלאכותית לצורך הקמת המשפחה החד- מינית. עם זאת, ניתן ללמוד רבות על גישת האורתודוקסיה משו"תים עכשוויים העוסקים בתופעת ההומוסקסואליות ובקיום מצוות הפריון במקרה זה. הדעה הרווחת היום בקרב הפוסקים הינה כי קשר חד- מיני אסור, כמו גם מיסודו וקיום מצוות פרו ורבו במסגרת זו. בשל כך ניתן להסיק כי הרבנים לא יתירו שימוש בהזרעה מלאכותית לצורך קיום מצוות הפריון במשפחה חד-מינית.
חלק חמישי- עמדת רבני הזרם רפורמי והקונסרבטיבי בשאלת ההזרעה המלאכותית
חלק זה מתמקד בזרמי היהדות הרפורמית והקונסרבטיבית ומציג את עמדות רבני זרמים אלו בעניין ההזרעה המלאכותית תוך עימותן עם עמדות פוסקים אורתודוקסיים.
פרק ראשון - עמדת הרבנות הרפורמית בשאלת ההזרעה המלאכותית
חשיבות מצוות הפריון מודגשת בספרות השו"ת הרפורמית, אולם טיפולי פוריות אינם מתפרשים כדרך היחידה לקיומה. על מנת שלא לפגוע במרקם החיים המשפחתי מוצעת לא אחת חלופת האימוץ לטיפולי פוריות מייגעים, תרומת זרע והיזקקות לפונדקאות ותרומת ביציות. שאלת השחתת הזרע, המעסיקה רבות את רבני הזרם האורתודוקסי, כמעט שאינה נידונה על ידי רבני הזרם הרפורמי. באשר לשאלות של כשרות וייחוס, רווחת הדעה בקרב רבנים רפורמיים בולטים כגון הרב הומולקה ורומיין, כי מעמד הממזרות איננו רלוונטי עוד בימינו ולכן ממילא לא נשקפת לילד הסכנה שזכויותיו הדתיות ייפגעו.
ועד הרבנים הרפורמיים התיר לחבריו לפעול לפי שיקול דעתם בעניין עריכת טקס נישואין דתי בין בני זוג בני אותו המין, תוך הדגשת הויכוח הפנימי בתנועה ומורת הרוח הקיימת מצד הזרמים האחרים ביהדות.
פרק שני - עמדת הרבנות הקונסרבטיבית בשאלת ההזרעה המלאכותית
עמדת רבני היהדות הקונסרבטיבית גורסת כי טיפולי פוריות מהווים רשות, אך אינם בגדר חובה עבור זוגות הרוצים לקיים את מצוות הפריה והרבייה ומתקשים בכך. בדומה לביטולה של גזירת הממזרות בזרם הרפורמי, בוטל מעמד זה לאחרונה גם ביהדות הקונסרבטיבית. אוננות במסגרת טיפולי פוריות הינה מותרת ואיננה מוגדרת כהשחתת זרע לבטלה ואף מותרת גם לשם תרומת זרע של יהודי לאישה לא יהודיה. כמו בזרם הרפורמי גם כאן מונחת אופציית האימוץ על סדר היום.
כנסת הרבנים הקונסרבטיבים בארצות הברית קיבלה החלטה ברוב זעום להכרה אזרחית בהומוסקסואלים, אך עם זאת השאירה על כנו את האיסור לקדש זוגות אלה. אין בהחלטה זו הכרה הלכתית בזוגיות החד-מינית אלא קבלתם החברתית של זוגות אלה ועידודם להשתלב בקהילות הקונסרבטיביות.
חלק שישי - סיכום ודיון בהשלכות המחקר
בחלקו השישי והאחרון בעבודת מחקר זו נסכם ונדון בהשלכותיה האתיות והגלובליולת של הפסיקה ההלכית בשאלה הנידונה.
כפי שניתן לראות מעבודת מחקר זו, הרבנים האורתודוקסיים מסתמכים בהכרעותיהם בעיקר על שיקולים הלכתיים ופחות על שיקולים אתיים ואוניברסליים. מחד, מסתייגים פוסקים אורתודוקסיים מסויימים משימוש לרעה בטיפולי פוריות, אך מאידך מוכנים הם בשם עקרונות דתיים להתיר שימוש בטכנולוגיות אלו במקרים שאינם מצריכים זאת משיקולים רפואיים. במיוחד בולט העדר התייחסותם של הפוסקים האורתודוקסיים לשיקולים מוסריים חברתיים, כמו גם לרצונה ולרווחתה של האישה העוברת טיפולי פוריות. לעומתם מביעים רבני הזרם הרפורמי והקונסרבטיבי את דאגתם להשלכותיהם של טיפולים אלו על נשים הנזקקות להתערבות רפואית מעין זו לשם התעברות ואלו העובדות בתעשיית הפריון. יש לציין כי הדיון ההלכתי עוסק בהיבט צר בלבד של שאלת ההזרעה המלאכותית ואינו נוגע ברבות מן השאלות המורכבות שמעוררות טכנולוגיות פריון מתקדמות. עם זאת הדיון ההלכתי הינו חשוב ביותר ומציף אף שאלות נוספות בדבר הסכנה הצפויה מהפיכתן של טכנולוגיות אלה לכלי שרת בידי אידאולוגיות דתיות או פוליטיות.
Galaxies are among the most complex systems that can currently be modelled with a computer. A realistic simulation must take into account cosmology and gravitation as well as effects of plasma, nuclear, and particle physics that occur on very different time, length, and energy scales. The Milky Way is the ideal test bench for such simulations, because we can observe millions of its individual stars whose kinematics and chemical composition are records of the evolution of our Galaxy. Thanks to the advent of multi-object spectroscopic surveys, we can systematically study stellar populations in a much larger volume of the Milky Way. While the wealth of new data will certainly revolutionise our picture of the formation and evolution of our Galaxy and galaxies in general, the big-data era of Galactic astronomy also confronts us with new observational, theoretical, and computational challenges.
This thesis aims at finding new observational constraints to test Milky-Way models, primarily based on infra-red spectroscopy from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) and asteroseismic data from the CoRoT mission. We compare our findings with chemical-evolution models and more sophisticated chemodynamical simulations. In particular we use the new powerful technique of combining asteroseismic and spectroscopic observations that allows us to test the time dimension of such models for the first time. With CoRoT and APOGEE (CoRoGEE) we can infer much more precise ages for distant field red-giant stars, opening up a new window for Galactic archaeology.
Another important aspect of this work is the forward-simulation approach that we pursued when interpreting these complex datasets and comparing them to chemodynamical models.
The first part of the thesis contains the first chemodynamical study conducted with the APOGEE survey. Our sample comprises more than 20,000 red-giant stars located within 6 kpc from the Sun, and thus greatly enlarges the Galactic volume covered with high-resolution spectroscopic observations. Because APOGEE is much less affected by interstellar dust extinction, the sample covers the disc regions very close to the Galactic plane that are typically avoided by optical surveys. This allows us to investigate the chemo-kinematic properties of the Milky Way's thin disc outside the solar vicinity. We measure, for the first time with high-resolution data, the radial metallicity gradient of the disc as a function of distance from the Galactic plane, demonstrating that the gradient flattens and even changes its sign for mid-plane distances greater than 1 kpc.
Furthermore, we detect a gap between the high- and low-[$\alpha$/Fe] sequences in the chemical-abundance diagram (associated with the thin and thick disc) that unlike in previous surveys can hardly be explained by selection effects. Using 6D kinematic information, we also present chemical-abundance diagrams cleaned from stars on kinematically hot orbits. The data allow us to confirm without doubt that the scale length of the (chemically-defined) thick disc is significantly shorter than that of the thin disc.
In the second part, we present our results of the first combination of asteroseismic and spectroscopic data in the context of Galactic Archaeology. We analyse APOGEE follow-up observations of 606 solar-like oscillating red giants in two CoRoT fields close to the Galactic plane. These stars cover a large radial range of the Galactic disc (4.5 kpc $\lesssim R_{\rm Gal}\lesssim15$ kpc) and a large age baseline (0.5 Gyr $\lesssim \tau\lesssim$ 13 Gyr), allowing us to study the age- and radius-dependence of the [$\alpha$/Fe] vs. [Fe/H] distributions. We find that the age distribution of the high-[$\alpha$/Fe] sequence appears to be broader than expected from a monolithically-formed old thick disc that stopped to form stars 10 Gyr ago. In particular, we discover a significant population of apparently young, [$\alpha$/Fe]-rich stars in the CoRoGEE data whose existence cannot be explained by standard chemical-evolution models. These peculiar stars are much more abundant in the inner CoRoT field LRc01 than in the outer-disc field LRc01, suggesting that at least part of this population has a chemical-evolution rather than a stellar-evolution origin, possibly due to a peculiar chemical-enrichment history of the inner disc. We also find that strong radial migration is needed to explain the abundance of super-metal-rich stars in the outer disc.
Finally, we use the CoRoGEE sample to study the time evolution of the radial metallicity gradient in the thin disc, an observable that has been the subject of observational and theoretical debate for more than 20 years. By dividing the CoRoGEE dataset into six age bins, performing a careful statistical analysis of the radial [Fe/H], [O/H], and [Mg/Fe] distributions, and accounting for the biases introduced by the observation strategy, we obtain reliable gradient measurements. The slope of the radial [Fe/H] gradient of the young red-giant population ($-0.058\pm0.008$ [stat.] $\pm0.003$ [syst.] dex/kpc) is consistent with recent Cepheid data. For the age range of $1-4$ Gyr, the gradient steepens slightly ($-0.066\pm0.007\pm0.002$ dex/kpc), before flattening again to reach a value of $\sim-0.03$ dex/kpc for stars with ages between 6 and 10 Gyr. This age dependence of the [Fe/H] gradient can be explained by a nearly constant negative [Fe/H] gradient of $\sim-0.07$ dex/kpc in the interstellar medium over the past 10 Gyr, together with stellar heating and migration. Radial migration also offers a new explanation for the puzzling observation that intermediate-age open clusters in the solar vicinity (unlike field stars) tend to have higher metallicities than their younger counterparts. We suggest that non-migrating clusters are more likely to be kinematically disrupted, which creates a bias towards high-metallicity migrators from the inner disc and may even steepen the intermediate-age cluster abundance gradient.
Aufgrund verschiedener wissenschaftlicher Erkenntnisse wird jungen Sporttreibenden vom Gebrauch von Nahrungsergänzungsmitteln (NEM) abgeraten. Diese Dissertation verfolgt vor dem Hintergrund der Theorie der Zielsysteme (TDZ) das Ziel der Erstellung anwendungsorientieren Handlungswissens, anhand dessen Interventionsempfehlungen zur Reduzierung des prävalenten NEM-Konsums im Nachwuchssport ableitbar sind. Insgesamt wurden sechs Untersuchungen durchgeführt. Die Versuchsteilnehmenden absolvierten in sämtlichen Studien eine Variante der lexikalischen Entscheidungsaufgabe. Diese Aufgabe diente der Operationalisierung von automatisch aktivier- und abrufbaren nahrungsergänzungsmittelbezogenen Ziel-Mittel-Relationen.
In einer Stichprobe von Sportstudierenden zeigte sich, dass NEM mit dem Ziel Leistung assoziiert sind (Studie 1). Unter Berücksichtigung des NEM-Konsums wurde dieses Ergebnis für Nachwuchsathletinnen und -athleten aus dem Breitensport repliziert (Studie 2). Zusätzlich konnte in beiden Studien die Bedeutung dieser Ziel-Mittel-Relationen für das Verhalten nachgewiesen werden. In den nachfolgenden Untersuchungen wurden spezifische Veränderungsmechanismen der verhaltensleitenden Ziel-Mittel-Relation aus Leistung und NEM zunächst an Sportstudierenden experimentell evaluiert. Durch das Herausstellen der fehlenden leistungssteigernden Wirkung von NEM konnte diese Zielassoziation nicht modifiziert werden (Studie 3). Das Betonen gesundheitsschädigender Konsequenzen (Studie 4) und das Akzentuieren einer gesunden Ernährung (Studie 5) erwiesen sich demgegenüber als geeignet zur Veränderung der Ziel-Mittel-Relation. Das Herausstellen einer gesunden Ernährung führte deskriptiv bei Nachwuchsathletinnen und -athleten ebenfalls zur Modifikation der Zielassoziation (Studie 6). Die inferenzstatistische Bestätigung der Ergebnisse dieser Studie steht aufgrund der geringen Teststärke der Untersuchung noch aus.
Insgesamt verdeutlichen die Ergebnisse, dass die auf Ebene automatischer Kognitionen bestehende und verhaltensleitende Assoziation des Gebrauchs von NEM mit Leistung durch die Akzentuierung gesundheitlicher Perspektiven experimentell verändert werden kann. Abschließend wird die theoretische und praktische Bedeutung des erstellten Handlungswissen für künftige Interventionsempfehlungen zur Reduzierung des Gebrauchs von NEM diskutiert.
Im Rahmen dieser Arbeit wurden zum einen erste Oligospiro(thio)ketal (OS(T)K)-basierte Modellsysteme (molekulare Sonden) für abstandsabhängige Messungen mittels Förster-Resonanz-Energietransfer (FRET) und zum anderen Sensorfluorophore, basierend auf einem DBD-Fluorophor und BAPTA, zur Messung der intrazellulären Calcium-Konzentration dargestellt.
Für die Synthese von molekularen Sonden für abstandsabhängige Messungen wurden verschiedenste einfach- und doppelt-markierte OS(T)K-Stäbe entwickelt und spektroskopisch untersucht. Die OS(T)K-Stäbe, sogenannte molekulare Stäbe, dienten als starre Abstandshalter zwischen den Fluorophoren. Als Fluorophore wurden Derivate von 6,7-Dihydroxy-4-methylcoumarin (Donor) und Acyl-DBD (Akzeptor) verwendet, die zusammen ein FRET-Paar bilden. Die Fluorophore wurden so funktionalisiert, dass sie sowohl unbeweglich bzw. „starr“, als auch beweglich bzw. „flexibel“ an den OS(T)K-Stab gebunden werden konnten. Für die Synthese der OS(T)K-Stäbe wurden ebenfalls eine Reihe an unterschiedlich langen und kurzen Stabbausteinen synthetisiert. Auf diese Weise wurden eine Vielzahl an verschiedensten einfach- und doppelt-markierten OS(T)K-Stäben dargestellt, deren Fluorophore sowohl „starr“ als auch „flexibel“ gebunden sind. Die dargestellten Stäbe wurden in verschiedensten Lösungsmitteln spektroskopisch untersucht, um anschließend das Verhalten in Vesikel, die eine biomimetische Umgebung darstellen, zu beurteilen. Es wurde festgestellt, dass sich die Stäbe erfolgreich in die Vesikelmembran einlagerten und hohe FRET-Effizienzen aufweisen.
Des Weiteren wurde ein FRET-Paar dargestellt, das sich durch 2-Photonenabsorpion im NIR-Bereich anregen lässt. Es wurde in den lebenden Zellen mittels Fluoreszenzlebenszeitmikroskopie (FLIM) untersucht.
Zur Untersuchung von intrazellulärem Calcium wurden zwei verschiedene DBD-Fluorophore über einen kurzen Linker mit dem Calcium-Chelator BAPTA verknüpft. Die dargestellten Fluorophore wurden sowohl in vitro als auch in vivo auf ihre Calcium-Sensitivität überprüft. Mittels FLIM wurden in lebenden Zellen die Fluoreszenzlebenszeitverteilungen der Fluorophore nach Calcium-Konzentrationsänderungen detektiert.
The work done during the PhD studies has been focused on measurements of distribution functions of rotating galaxies using integral field spectroscopy observations.
Throughout the main body of research presented here we have been using CALIFA (Calar Alto Legacy Integral Field Area) survey stellar velocity fields to obtain robust measurements of circular velocities for rotating galaxies of all morphological types. A crucial part of the work was enabled by well-defined CALIFA sample selection criteria: it enabled reconstructing sample-independent distributions of galaxy properties.
In Chapter 2, we measure the distribution in absolute magnitude - circular velocity space for a well-defined sample of 199 rotating CALIFA galaxies using their stellar kinematics. Our aim in this analysis is to avoid subjective selection criteria and to take volume and large-scale structure factors into account. Using stellar velocity fields instead of gas emission line kinematics allows including rapidly rotating early type galaxies. Our initial sample contains 277 galaxies with available stellar velocity fields and growth curve r-band photometry. After rejecting 51 velocity fields that could not be modelled due to the low number of bins, foreground contamination or significant interaction we perform Markov Chain Monte Carlo (MCMC) modelling of the velocity fields, obtaining the rotation curve and kinematic parameters and their realistic uncertainties. We perform an extinction correction and calculate the circular velocity v_circ accounting for pressure support a given galaxy has. The resulting galaxy distribution on the M_r - v_circ plane is then modelled as a mixture of two distinct populations, allowing robust and reproducible rejection of outliers, a significant fraction of which are slow rotators. The selection effects are understood well enough that the incompleteness of the sample can be corrected and the 199 galaxies can be weighted by volume and large-scale structure factors enabling us to fit a volume-corrected Tully-Fisher relation (TFR). More importantly, we also provide the volume-corrected distribution of galaxies in the M_r - v_circ plane, which can be compared with cosmological simulations. The joint distribution of the luminosity and circular velocity space densities, representative over the range of -20 > M_r > -22 mag, can place more stringent constraints on the galaxy formation and evolution scenarios than linear TFR fit parameters or the luminosity function alone.
In Chapter 3, we measure one of the marginal distributions of the M_r - v_circ distribution: the circular velocity function of rotating galaxies. The velocity function is a fundamental observable statistic of the galaxy population, being of a similar importance as the luminosity function, but much more difficult to measure. We present the first directly measured circular velocity function that is representative between 60 < v_circ < 320 km s^-1 for galaxies of all morphological types at a given rotation velocity. For the low mass galaxy population 60 < v_circ < 170 km s^-1, we use the HIPASS velocity function. For the massive galaxy population 170 < v_circ < 320 km s^-1, we use stellar circular velocities from CALIFA. The CALIFA velocity function includes homogeneous velocity measurements of both late and early-type rotation-supported galaxies. It has the crucial advantage of not missing gas-poor massive ellipticals that HI surveys are blind to. We show that both velocity functions can be combined in a seamless manner, as their ranges of validity overlap. The resulting observed velocity function is compared to velocity functions derived from cosmological simulations of the z = 0 galaxy population. We find that dark matter-only simulations show a strong mismatch with the observed VF. Hydrodynamic Illustris simulations fare better, but still do not fully reproduce observations.
In Chapter 4, we present some other work done during the PhD studies, namely, a method that improves the precision of specific angular measurements by combining simultaneous Markov Chain Monte Carlo modelling of ionised gas 2D velocity fields and HI linewidths. To test the method we use a sample of 25 galaxies from the Sydney-AAO Multi-object Integral field (SAMI) survey that had matching ALFALFA HI linewidths. Such a method allows constraining the rotation curve both in the inner regions of a galaxy and in its outskirts, leading to increased precision of specific angular momentum measurements. It could be used to further constrain the observed relation between galaxy mass, specific angular momentum and morphology (Obreschkow & Glazebrook 2014).
Mathematical and computational methods are presented in the appendices.
Menschen mit chronisch entzündlichen Darmerkrankungen (CED) leiden unter vielfältigen körperlichen und psychosozialen Einschränkungen. Wie auch bei anderen chronischen Erkrankungen könnten Patientenschulungen ihr psychisches Befinden verbessern (z.B. De Ridder & Schreurs, 2001; Faller, Reusch & Meng, 2011a; Küver, Becker & Ludt, 2008; Schüssler, 1998; Warsi, Wang, LaValley, Avorn & Solomon, 2004). Für CED liegen jedoch nur wenige Schulungsevaluationen vor (z.B. Bregenzer et al., 2005; Mussell, Böcker, Nagel, Olbrich & Singer, 2003; Oxelmark, Magnusson, Löfberg & Hillerås, 2007), deren Aussagekraft i.d.R. durch methodische Mängel eingeschränkt ist. Daher ist die Bedeutung von Schulungsprogrammen für CED-Betroffene weiterhin offen. Überdies gibt es für den deutschen Sprachraum noch keine Schulung, die zu psychischen Verbesserungen führt. Aus diesem Grunde wurde ein 1,5-tägiges Wochenend-Seminar mit medizinischen und psychologischen Inhalten konzeptionalisiert, manualisiert und in der vorliegenden Studie evaluiert.
Zur summativen Evaluation nahmen 181 ambulante CED-Patienten an einer prospektiven, multizentrischen, randomisierten, kontrollierten Studie mit vier Messzeitpunkten teil: vor (T1), zwei Wochen (T2) und drei Monate (T3) nach dem Seminar. Zur 12-Monatskatamnese (T4EG) wurde die Stabilität der Effekte in der Experimentalgruppe (EG; n = 86) überprüft. Die Wartekontrollgruppe (n = 95) erhielt zunächst die Standardbehandlung, also keine Patientenschulung, und konnte an dieser nach der dritten Datenerhebung ebenfalls teilnehmen. Kovarianzanalysen (ANCOVAs) mit Kontrolle für die jeweilige Ausgangslage wurden durchgeführt. Weitere Analysen legten eine Adjustierung für die Krankheitsaktivität zu T1 nahe, weshalb diese als zusätzliche Kovariate in die ANCOVAs aufgenommen wurde. Krankheitsbezogene Ängste und Sorgen (PS-CEDE Gesamtwert zu T3; Krebs, Kachel & Faller, 1998) fungierten als primärer Zielparameter. Zu den sekundären Zielkriterien gehörten Progredienzangst und Angstbewältigung (PA-F-KF und PA-F; Mehnert, Herschbach, Berg, Henrich & Koch, 2006 bzw. Dankert et al., 2003; Herschbach et al., 2005) sowie die Gesundheitskompetenzen Positive Grundhaltung, Aktive Lebensgestaltung und Erwerb von Fertigkeiten und Handlungsstrategien (heiQ; Osborne, Elsworth & Whitfield, 2007; Schuler et al., 2013). Weitere sekundäre Zielparameter waren gesundheitsbezogene Lebensqualität (SF-12; Bullinger & Kirchberger, 1998), Symptome einer Angststörung oder Depression (PHQ-4; Kroenke, Spitzer, Williams & Löwe, 2009; Löwe et al., 2010), Wissen, der Umgang mit der CED bzw. von ihr ausgelösten negativen Gefühlen sowie die Zufriedenheit der Teilnehmenden mit dem Seminar. Von Interesse war außerdem, ob Geschlecht, Alter, Art, Dauer oder Aktivität der Erkrankung vor der Schulung einen Einfluss auf die genannten Variablen hatten und ob für sie differentielle Wirksamkeitseffekte bestanden. Darüber hinaus wurden krankheitsbezogene Ängste und Sorgen von ungeschulten Studienteilnehmern untersucht.
Zwei Wochen und drei Monate nach der Schulung ließen sich im Vergleich von Experimental- und Kontrollgruppe signifikante, mittlere bis große Effekte auf krankheitsbezogene Ängste und Sorgen, Progredienzangst und deren Bewältigung sowie eine Positive Grundhaltung der CED gegenüber erzielen (stets p ≤ .001). Außerdem kam es zu beiden Messzeitpunkten zu signifikanten, großen Interventionseffekten auf den Erwerb von Fertigkeiten und Handlungsstrategien im Umgang mit der Erkrankung, das Wissen um sie und den Umgang mit ihr (stets p < .001) sowie zu moderaten Effekten auf den Umgang mit CED-bedingten negativen Gefühlen (T2: p = .001; T3: p = .008). Alle beschriebenen Effekte waren auch nach zwölf Monaten noch stabil. Für Aktive Lebensgestaltung, gesundheitsbezogene Lebensqualität sowie Angst- und Depressionssymptomatik konnten keine Schulungseffekte nachgewiesen werden.
Die zusätzliche Kontrolle für die Krankheitsaktivität zu T1 führte zu keinen wesentlichen Änderungen in den Ergebnissen. Auch bei den Subgruppenanalysen hatte die Krankheitsaktivität keinen relevanten Einfluss auf die Wirksamkeit der Schulung. Gleiches gilt für Geschlecht, Alter, Art und Dauer der CED. Mit Ausnahme der Krankheitsaktivität deuteten dies bereits die zur Baseline durchgeführten t-Tests an, bei denen insgesamt nur sehr wenige signifikante, höchstens moderate Unterschiede zwischen den einzelnen Subgruppen auftraten.
Sowohl bei der formativen als auch der summativen Evaluation zeigte sich überdies die hohe Zufriedenheit der Teilnehmenden mit der Schulung. Neben der Akzeptanz konnte außerdem die Durchführbarkeit bestätigt werden. Die Auswertung der Ängste und Sorgen der Studienteilnehmenden lieferte zudem Hinweise für die Entwicklung und Modifikation von Interventionen für CED-Betroffene.
Es lässt sich festhalten, dass für die hier evaluierte Schulung für CED-Patienten ein Wirksamkeitsnachweis erbracht werden konnte und sie sehr positiv von den Teilnehmenden bewertet wurde. Sie führte sowohl kurz-, mittel- als auch langfristig zu substantiellen Verbesserungen in psychischer Belastung, Selbstmanagement-Fähigkeiten, der Bewältigung der Erkrankung sowie im Wissen und war gleichermaßen wirksam bei Betroffenen, die sich in Geschlecht, Alter, Art, Dauer oder Aktivität ihrer CED unterschieden.
In Zeiten eines sich schnell ändernden und vielseitigen Energiemarktes müssen Kohlenstoffmaterialien für verschiedene Anforderungen einsetzbar sein. Dies erfordert flexibel synthetisierbare Kohlenstoffmaterialien bevorzugt aus günstigen und nachhaltigen Kohlenstoffquellen. Es ist allerdings nicht leicht Vorläuferverbindungen auszumachen, welche sich einerseits für verschiedene Herstellungsverfahren eignen und deren Kohlenstoffprodukte andererseits in spezifischen Eigenschaften, wie der Struktur, des Stickstoffanteils, der Oberfläche und der Porengrößen, eingestellt werden können. In diesem Zusammenhang können natürliche Polyphenole, etwa überschüssige Tannine aus der Weinproduktion, eine neue Welt zu hoch funktionalen und vielseitig einstellbaren Kohlenstoffmaterialien mit hohen Ausbeuten öffnen.
Das Hauptziel dieser vorliegenden Thesis war es neue funktionale, einstellbare und skalierbare nanostrukturierte Kohlenstoffmaterialien aus Tanninen (insbesondere Tanninsäure) für unterschiedliche elektrochemische Zwecke zu synthetisieren und zu charakterisieren. Ermöglicht wurde dies durch unterschiedliche synthetische Herangehensweisen, wie etwa der polymeren Strukturdirektion, dem ionothermalen Templatieren und der weichen Templatierung. An Stelle des weitläufig gebräuchlichen, aber kanzerogenen Vernetzungsagens Formaldehyd wurden bei den vorgestellten Synthesen Harnstoff und Thioharnstoff gewählt, um zugleich die synthetisierten Kohlenmaterialien variabel dotieren zu können.
Daher wurden im ersten Teil der Arbeit die Wechselwirkungen, Reaktionen und thermischen Verhaltensweisen von Tanninsäure und Mixturen von Tanninsäure und Harnstoff bzw. Thioharnstoff untersucht, um daraus wichtige Erkenntnisse für die verschiedenen Kohlenstoffsynthesen zu gewinnen.
Durch die Verwendung eines polymeren Strukturierungsagenz Pluronic P123 konnten in einer ersten Kohlenstoffsynthese nachhaltige und dotierbare Kohlenstoffpartikel mit Durchmessern im Nanometerbereich aus Tanninsäure und Harnstoff hergestellt werden. Es konnte dabei gezeigt werden, dass durch die Modifikation der verschiedenen Syntheseparameter die Kohlenstoffnanopartikel gemäß ihres gemittelten Partikeldurchmessers, ihrer BET-Oberfläche, ihrer Komposition, ihrer Leitfähigkeit und ihrer chemischen Stabilität einstellbar sind. Dies eröffnete die Möglichkeit diese Kohlenstoffpartikel als alternatives und nachhaltiges Rußmaterial einzusetzen.
Weiterhin war es durch die ionothermale Templatierung möglich poröse, dotierte und kontrollierbare Kohlenstoffpartikel mit hohen spezifischen Oberflächen aus den gewählten Präkursorverbindungen zu synthetisieren, die sich für den Einsatz in Superkondensatoren eignen.
Auf diesen Erkenntnissen aufbauend konnten mittels der Rotationsbeschichtung poröse binderfreie und strukturierte Kohlenstofffilme synthetisiert werden, die eine spinodale Struktur aufwiesen. Anhand der Modifikation der Stammlösungskonzentration, der Rotationsgeschwindigkeit und der verwendeten Substrate konnten die Filmdicke (100-1000 nm), die Morphologie und Gesamtoberfläche gezielt beeinflusst werden. Die erweiterte elektrochemische Analyse zeigte außerdem ein sehr gut zugängliches Porensystem der porösen Kohlenstofffilme.
Allumfassend konnten demnach verschiedene Synthesewege für Kohlenstoffmaterialien aus Tanninen aufgezeigt werden, die verschiedenartig strukturiert und kontrolliert werden können und sich für diverse Anwendungsgebiete eignen.
Nowadays, graph data models are employed, when relationships between entities have to be stored and are in the scope of queries. For each entity, this graph data model locally stores relationships to adjacent entities. Users employ graph queries to query and modify these entities and relationships. These graph queries employ graph patterns to lookup all subgraphs in the graph data that satisfy certain graph structures. These subgraphs are called graph pattern matches. However, this graph pattern matching is NP-complete for subgraph isomorphism. Thus, graph queries can suffer a long response time, when the number of entities and relationships in the graph data or the graph patterns increases.
One possibility to improve the graph query performance is to employ graph views that keep ready graph pattern matches for complex graph queries for later retrieval. However, these graph views must be maintained by means of an incremental graph pattern matching to keep them consistent with the graph data from which they are derived, when the graph data changes. This maintenance adds subgraphs that satisfy a graph pattern to the graph views and removes subgraphs that do not satisfy a graph pattern anymore from the graph views.
Current approaches for incremental graph pattern matching employ Rete networks. Rete networks are discrimination networks that enumerate and maintain all graph pattern matches of certain graph queries by employing a network of condition tests, which implement partial graph patterns that together constitute the overall graph query. Each condition test stores all subgraphs that satisfy the partial graph pattern. Thus, Rete networks suffer high memory consumptions, because they store a large number of partial graph pattern matches. But, especially these partial graph pattern matches enable Rete networks to update the stored graph pattern matches efficiently, because the network maintenance exploits the already stored partial graph pattern matches to find new graph pattern matches. However, other kinds of discrimination networks exist that can perform better in time and space than Rete networks. Currently, these other kinds of networks are not used for incremental graph pattern matching.
This thesis employs generalized discrimination networks for incremental graph pattern matching. These discrimination networks permit a generalized network structure of condition tests to enable users to steer the trade-off between memory consumption and execution time for the incremental graph pattern matching. For that purpose, this thesis contributes a modeling language for the effective definition of generalized discrimination networks. Furthermore, this thesis contributes an efficient and scalable incremental maintenance algorithm, which updates the (partial) graph pattern matches that are stored by each condition test. Moreover, this thesis provides a modeling evaluation, which shows that the proposed modeling language enables the effective modeling of generalized discrimination networks. Furthermore, this thesis provides a performance evaluation, which shows that a) the incremental maintenance algorithm scales, when the graph data becomes large, and b) the generalized discrimination network structures can outperform Rete network structures in time and space at the same time for incremental graph pattern matching.
In der vorliegenden Arbeit wurden verschiedene Polymere hergestellt, die bestimmte funktionelle Gruppen beinhalten. Diese Gruppen werden zum Teil durch Alkylketten geschützt, zum Teil liegen sie ungeschützt im Polymer vor. Mit diesen Polymeren wurden Untersuchungen mit knochenähnlichen Materialien sogenanntem Calciumphosphat durchgeführt. Es wurde der Einfluss der verschiedenen Polymere auf die Bildung dieser knochenähnlichen Substanzen untersucht und auch der Einfluss auf die Stabilität und das Auflösungsverhalten der Calciumphosphate. Dabei sollte ein besonderes Augenmerk auf die funktionellen Gruppen, sogenannte Phosphonsäuren und deren Ester, die die Phosphonsäuren schützen, gesetzt werden. Es stellte sich heraus, dass bei der Bildung der knochenähnlichen Materialien die Polymere mit Estergruppen eine leichte Förderung der Calciumphosphat-Bildung verursachen, während die ungeschützten Polymere die Bildung des „Knochenmaterials“ sehr stark verzögern. Dieser Effekt verstärkt sich noch, wenn eine weitere bestimmte Komponente zum Polymer hinzukommt und somit ein Copolymer gebildet wird. Diese Copolymere beschleunigen bzw. verlangsamen die Calciumphosphatbildung noch stärker. Werden Polymere mit einem anderen Polymergerüst aber den gleichen Phosphonsäuresetern in den Seitenketten verwendet, ändert sich der Einfluss der Calciumphosphat-Bildung wenig. Verglichen mit Polymeren ohne solche Phosphonsäuregruppen wird erkennbar, dass es weniger die Phosphonsäuregruppe ist, die die Mineralisation beeinflusst, sondern es eher eine Folge der Säure im Polymer ist.
Wird die Stabilisierung und Auflösung der Knochenähnlichen Substanzen betrachtet, fällt auf, dass auch hier wieder die Säuren den größten Effekt ausüben. Die Phosphonsäuregruppen scheinen dabei jedoch tatsächlich einen besonderen Effekt auszuüben, da bei diesen die Stabilisierung und auch das Auflösungsvermögen von Calciumphospaht von allen untersuchten Polymeren am größten sind.
In der Arbeit konnte außerdem gezeigt werden, dass die Polymere und Copolymere mit Phosphonsäuregruppen einen leicht positiven Effekt auf die Zahngesundheit zeigen. Die Zahl von Bakterien auf der Zahnoberfläche konnte reduziert werden und bei der Untersuchung der Zahnauflösung wurde eine glattere Zahnoberfläche erhalten, jedoch wurde auch mit den untersuchten Polymeren der Zahn im Inneren angegriffen. Weitere Untersuchungen können hier noch genaueren Aufschluss geben. Außerdem sollten auch die Polymere mit dem unterschiedlichen Polymergerüst und Phosphonsäureestergruppen untersucht werden.
Letztere Polymere wurden verwendet, um festere “gelartige“ Polymernetzwerke herzustellen und deren Einfluss auf die Calciumphosphatmineralisation zu untersuchen. Es stellte sich heraus, dass ohne das Einbetten einiger Calciumphosphatteilchen keine Bildung von Calciumphospaht an den Materialien ausgelöst wurde, wurden die sogenannten Hydrogele jedoch mit Calciumphosphatpartikeln geimpft, konnte deutliches weiteres Calciumphosphatwachstum beobachtet werden. Das Material lässt sich auch in verschiedene Formen bringen. Somit könnte das System nach weiteren Untersuchungen zur Verträglichkeit mit Zellen oder Geweben ein mögliches Material für Implantate darstellen, mit denen gezielt Knochenwachstum eingeleitet werden könnte.
The valorization of carbohydrates is one of the most promising fields in green chemistry, as it enables to produce bulk chemicals and fuels out of renewable and abundant resources, instead of further exploiting fossil feedstocks. The focus in this thesis is the conversion of fructose, using dehydration and hydrodeoxygenation reactions. The main goal is to find an easy continuous process, including the solubility of the sugar in a green solvent, the conversion over a solid acid as well as over a metal@tungsten carbide catalyst.
At the beginning of this thesis, solid acid catalysts are synthesized by using carbohydrate material like glucose and starch at high temperatures (up to 600 °C). Additionally a third carbon is synthesized, using an activation method based on Ca(OH)2. After carbonization and further sulfonation, using fuming sulfuric acid, the three resulting catalysts are characterized together with sulfonated carbon black and Amberlyst 15 as references. In order to test all solid acid catalysts in reaction, a 250 mm x 4.6 mm stainless steel column is used as a fixed-bed continuous reactor. The temperature (110 °C to 250 °C) and residence time (2 to 30 minutes) is varied, and a direct relationship between contact time and selectivity is determined. The reaction mechanism, as well as the product distribution is showing a dehydration step of fructose towards 5-hydroxymethylfurfural (HMF). These furan-ring molecules are considered as “sleeping giants”, due to the possibility of using them as fuel, but also for upgrading them to chemicals like terephthalic acid or p-xylene. Consecutive reactions are producing levulinic acid, as well as condensation products with ethanol and formic acid. The activated carbon is additionally showing a 2 % yield of 2,5-Dimethylfuran (DMF) production, pointing towards the extraordinary properties of this catalyst. Without a metal catalyst present, what is normally necessary for hydrogenation reactions, a transferhydrogenation (with formic acid) is observed. The active catalyst was therefore carbon itself, what activated the hydrogen on its surface. This phenomenon was just very rarely observed so far. Expensive noble metals are the material of choice, when it comes to hydrogenation reactions nowadays and cheaper alternatives are necessary.
By postulating a similar electronic structure of tungsten carbide (WC) to platinum by Lewy and Boudart, research is focusing on the replacement of Pt. The production of nano-sized tungsten carbide particles (7.5 ± 2.5 nm, 70 m2 g-1) is enabled by the so called “urea glass route” and its catalytic performances are compared to commercial material. It is shown, that the activity is strongly dependent on the size of the particles as well as the surface area. Nano-sized tungsten carbide is showing activity for hydrogenation reactions under mild conditions (maximum 150 °C, 30 bar). This material therefore opens up new possibilities for replacing the rare and expensive platinum with tungsten carbide based catalysts.
Additionally different metal nanoparticles of palladium, copper and nickel are deposited on top of WC to further promote its reactivity. The nickel nanoparticles are strongly connected to WC and showed the best activity as well as selectivity for upgrading HMF with hydrodeoxygenation. The Ni@WC is not leaching and is showing very good hydrodeoxygenation properties with DMF yields up to 90 percent. Copper@WC is not showing good activity and palladium@WC enables undesired consecutive reactions, hydrogenating the furan ring system.
In order to enable the upgrade of fructose to DMF directly in a continuous system, the current H CUBE Pro TM hydrogenation system is customized with a second reaction column. A 250 mm x 4.6 mm stainless steel reactor column is connected ahead of the hydrogen insertion, enabling the dehydration of fructose to HMF derivatives, before pumping these products into the second column for hydrogenation. The overall residence time in the two column reactor system is 14 minutes. The overall results are an almost full conversion with a yield of 38.5 % DMF and 47 % yield of EL. The main disadvantage is the formation of higher mass products, so called humins, which start depositing on top of the catalysts, blocking their active sites.
In general it can be stated, that a two column system goes along with a higher investment as well as more maintenance costs, compared to a one column catalytic approach. To develop a catalyst, which is on the one hand able to dehydrate as well as hydrodeoxygenate the reactants, is aimed for at the last part of the thesis. The activated carbon however shows already activity for hydrodeoxygenation without any metal present and offers itself therefore as an alternative to overcome the temperature instability of Amberlyst 15 (max. 120 °C) for a combined DMF production directly from fructose. The activity for the upgrade to DMF is increased from 2 % to 12 % DMF yield in one mixed continuous column.
In order to scale up the entire one column approach, an 800 mm x 28.5 mm inner diameter column was planned and manufactured. The system is scaled up and assembled, whereas this flow reactor system is able to be run with 50 mL min-1 maximum flow rate, to stand a pressure of maximum 100 bar and be heated to around 500 °C. The tubing and connections, as well as the used devices are planned according to be safe and easy in use. The scaled-up approach offers a reaction column 120 times bigger (510 ml) then the first extension of the commercial system. This further extension offers the possibility of ranging between 1 and 1000 mL min-1, making it possible to use the approach in pilot plant applications.
According to the classical plume hypothesis, mantle plumes are localized upwellings of hot, buoyant material in the Earth’s mantle. They have a typical mushroom shape, consisting of a large plume head, which is associated with the formation of voluminous flood basalts (a Large
Igneous Province) and a narrow plume tail, which generates a linear, age-progressive chain of volcanic edifices (a hotspot track) as the tectonic plate migrates over the relatively stationary plume. Both plume heads and tails reshape large areas of the Earth’s surface over many tens of millions of years.
However, not every plume has left an exemplary record that supports the classical hypothesis. The main objective of this thesis is therefore to study how specific hotspots have created the crustal thickness pattern attributed to their volcanic activities. Using regional geodynamic
models, the main chapters of this thesis address the challenge of deciphering the three individual (and increasingly complex) Réunion, Iceland, and Kerguelen hotspot histories, especially focussing on the interactions between the respective plume and nearby spreading ridges.
For this purpose, the mantle convection code ASPECT is used to set up three-dimensional numerical models, which consider the specific local surroundings of each plume by prescribing time-dependent boundary conditions for temperature and mantle flow. Combining reconstructed plate boundaries and plate motions, large-scale global flow velocities and an inhomogeneous lithosphere thickness distribution together with a dehydration rheology represents a novel setup for regional convection models.
The model results show the crustal thickness pattern produced by the plume, which is compared to present-day topographic structures, crustal thickness estimates and age determinations of volcanic provinces associated with hotspot activity. Altogether, the model results agree well
with surface observations. Moreover, the dynamic development of the plumes in the models provide explanations for the generation of smaller, yet characteristic volcanic features that were previously unexplained. Considering the present-day state of a model as a prediction for the
current temperature distribution in the mantle, it cannot only be compared to observations on the surface, but also to structures in the Earth’s interior as imaged by seismic tomography.
More precisely, in the case of the Réunion hotspot, the model demonstrates how the distinctive gap between the Maldives and Chagos is generated due to the combination of the ridge geometry and plume-ridge interaction. Further, the Rodrigues Ridge is formed as the surface expression
of a long-distance sublithospheric flow channel between the upwelling plume and the closest ridge segment, confirming the long-standing hypothesis of Morgan (1978) for the first time in a dynamic context. The Réunion plume has been studied in connection with the seismological
RHUM-RUM project, which has recently provided new seismic tomography images that yield an excellent match with the geodynamic model.
Regarding the Iceland plume, the numerical model shows how plume material may have accumulated in an east-west trending corridor of thin lithosphere across Greenland and resulted in simultaneous melt generation west and east of Greenland. This provides an explanation for the
extremely widespread volcanic material attributed to magma production of the Iceland hotspot and demonstrates that the model setup is also able to explain more complicated hotspot histories. The Iceland model results also agree well with newly derived seismic tomographic images.
The Kerguelen hotspot has an extremely complex history and previous studies concluded that the plume might be dismembered or influenced by solitary waves in its conduit to produce the reconstructed variable melt production rate. The geodynamic model, however, shows that a constant plume influx can result in a variable magma production rate if the plume interacts with nearby mid-ocean ridges. Moreover, the Ninetyeast Ridge in the model is created by on-ridge activities, while the Kerguelen plume was located beneath the Australian plate. This is also a contrast to earlier studies, which described the Ninetyeast Ridge as the result of the Indian plate passing over the plume. Furthermore, the Amsterdam-Saint Paul Plateau in the model is the result of plume material flowing from the upwelling toward the Southeast Indian Ridge, whereas previous geochemical studies attributed that volcanic province to a separate deep plume.
In summary, the three case studies presented in this thesis consistently highlight the importance of plume-ridge interaction in order to reconstruct the overall volcanic hotspot record as well as specific smaller features attributed to a certain hotspot. They also demonstrate that it is not necessary to attribute highly complicated properties to a specific plume in order to account for complex observations. Thus, this thesis contributes to the general understanding of plume dynamics and extends the very specific knowledge about the Réunion, Iceland, and Kerguelen mantle plumes.
Estuarine marshes are ecosystems that are situated at the transition zone between land and water and are thus controlled by physical and biological interactions. Marsh vegetation offers important ecosystem services by filtrating solid and dissolved substances from the water and providing habitat. By buffering a large part of the arriving flow velocity, attenuating wave energy and serving as erosion control for riverbanks, tidal marshes furthermore reduce the destructive effects of storm surges and storm waves and thus contribute to ecosystem-based shore protection. However, in many estuaries, extensive embankments, artificial bank protection, river dredging and agriculture threaten tidal marshes. Global warming might entail additional risks, such as changes in water levels, an increase of the tidal amplitude and a resulting shift of the salinity zones. This can affect the dynamics of the shore and foreland vegetation, and vegetation belts can be narrowed or fragmented. Against this background, it is crucial to gain a better understanding of the processes underlying the spatio temporal vegetation dynamics in brackish marshes. Furthermore, a better understanding of how plant-habitat relationships generate patterns in tidal marsh vegetation is vital to maintain ecosystem functions and assess the response of marshes to environmental change as well as the success of engineering and restoration projects.
For this purpose, three research objectives were addressed within this thesis: (1) to explore the possibility of vegetation serving as self-adaptive shore protection by quantifying the reduction of current velocity in the vegetation belt and the morphologic plasticity of a brackish marsh pioneer, (2) to disentangle the roles of abiotic factors and interspecific competition on species distribution and stand characteristics in brackish marshes, and (3) to develop a mechanistic vegetation model that helps analysing the influence of habitat conditions on the spatio-temporal dynamic of tidal marsh vegetation. These aspects were investigated using a combination of field studies and statistical as well as process-based modelling.
To explore the possibility of vegetation serving as self-adaptive coastal protection, in the first study, we measured current velocity with and without living vegetation, recorded ramet density and plant thickness during two growing periods at two locations in the Elbe estuary and assessed the adaptive value of a larger stem diameter of plants at locations with higher mechanical stress by biomechanical measurements. The results of this study show that under non-storm conditions, the vegetation belt of the marsh pioneer Bolboschoenus maritimus is able to buffer a large proportion of the flow velocity. We were furthermore able to show that morphological traits of plant species are adapted to hydrodynamic forces by demonstrating a positive correlation between ramet thickness and cross-shore current. In addition, our measurements revealed that thicker ramets growing at the front of the vegetation belt have a significantly higher stability than ramets inside the vegetation belt. This self-adaptive effect improves the ability of B. maritimus to grow and persist in the pioneer zone and could provide an adaptive value in habitats with high mechanical stress.
In the second study, we assessed the distribution of the two marsh species and a set of stand characteristics, namely aboveground and belowground biomass, ramet density, ramet height and the percentage of flowering ramets. Furthermore, we collected information on several abiotic habitat factors to test their effect on plant growth and zonation with generalised linear models (GLMs). Our results demonstrate that flow velocity is the main factor controlling the distribution of Bolboschoenus maritimus and Phragmites australis. Additionally, inundation height and duration, as well as intraspecific competition affect distribution patterns. This study furthermore shows that cross-shore flow velocity does not only directly influence the distribution of the two marsh species, but also alters the plants’ occurrence relative to inun-dation height and duration. This suggests an effect of cross-shore flow velocity on their tolerance to inundation. The analysis of the measured stand characteristics revealed a negative effect of total flow velocity on all measured parameters of B. maritimus and thus confirmed our expectation that flow velocity is a decisive stressor which influences the growth of this species.
To gain a better understanding of the processes and habitat factors influencing the spatio-temporal vegetation dynamics in brackish marshes, I built a spatially explicit, mechanistic model applying a pattern-oriented modelling approach. A sensitivity analysis of the para-meters of this dynamic habitat-macrophyte model HaMac suggests that rhizome growth is the key process for the lateral dynamics of brackish marshes. From the analysed habitat factors, P. australis patterns were mainly influenced by flow velocity. The competition with P. australis was of key importance for the belowground biomass of B. maritimus. Concerning vegetation dynamics, the model results emphasise that without the effect of flow velocity the B. maritimus vegetation belt would expand into the tidal flat at locations with present vegetation recession, suggesting that flow velocity is the main reason for vegetation recession at exposed locations.
Overall, the results of this thesis demonstrate that brackish marsh vegetation considerably contributes to flow reduction under average flow conditions and can hence be a valuable component of shore-protection schemes. At the same time, the distribution, growth and expansion of tidal marsh vegetation is substantially influenced by flow. Altogether, this thesis provides a clear step forward in understanding plant-habitat interactions in tidal marshes. Future research should integrate studies of vertical marsh accretion with research on the factors that control the lateral position of marshes.
This project was focused on generating ultra thin stimuli responsive membranes with an embedded transmembrane protein to act as the pore. The membranes were formed by crosslinking of transmembrane protein polymer conjugates. The conjugates were self assembled on air water interface and the polymer chains crosslinked using a UV crosslinkable comonomer to engender the membrane. The protein used for the studies reported herein was one of the largest transmembrane channel proteins, ferric hydroxamate uptake protein component A (FhuA), found in the outer membrane of Escherichia coli (E. coli). The wild type protein and three genetic variants of FhuA were provided by the group of Prof. Schwaneberg in Aachen. The well known thermo responsive poly(N isopropylacrylamide) (PNIPAAm) and the pH and thermo responsive polymer poly((2-dimethylamino)ethyl methacrylate) (PDMAEMA) were conjugated to FhuA and the genetic variants via controlled radical polymerization (CRP) using grafting from technique. These polymers were chosen because they would provide stimuli handles in the resulting membranes. The reported polymerization was the first ever attempt to attach polymer chains onto a membrane protein using site specific modification.
The conjugate synthesis was carried out in two steps – a) FhuA was first converted into a macroinitiator by covalently linking a water soluble functional CRP initiator to the lysine residues. b) Copper mediated CRP was then carried out in pure buffer conditions with and without sacrificial initiator to generate the conjugates.
The challenge was carrying out the modifications on FhuA without denaturing it. FhuA, being a transmembrane protein, requires amphiphilic species to stabilize its highly hydrophobic transmembrane region. For the experiments reported in this thesis, the stabilizing agent was 2 methyl 2,4-pentanediol (MPD). Since the buffer containing MPD cannot be considered a purely aqueous system, and also because MPD might interfere with the polymerization procedure, the reaction conditions were first optimized using a model globular protein, bovine serum albumin (BSA). The optimum conditions were then used for the generation of conjugates with FhuA.
The generated conjugates were shown to be highly interfacially active and this property was exploited to let them self assemble onto polar apolar interfaces. The emulsions stabilized by particles or conjugates are referred to as Pickering emulsions. Crosslinking conjugates with a UV crosslinkable co monomer afforded nano thin micro compartments. Interfacial self assembly at the air water interface and subsequent UV crosslinking also yielded nano thin, stimuli responsive membranes which were shown to be mechanically robust. Initial characterization of the flux and permeation of water through these membranes is also reported herein. The generated nano thin membranes with PNIPAAm showed reduced permeation at elevated temperatures owing to the resistance by the hydrophobic and thus water-impermeable polymer matrix, hence confirming the stimulus responsivity.
Additionally, as a part of collaborative work with Dr. Changzhu Wu, TU Dresden, conjugates of three enzymes with current/potential industrial relevance (candida antarctica lipase B, benzaldehyde lyase and glucose oxidase) with stimuli responsive polymers were synthesized. This work aims at carrying out cascade reactions in the Pickering emulsions generated by self assembled enzyme polymer conjugate.
In this era of high-speed informatization and globalization, online education is no longer an exquisite concept in the ivory tower, but a rapidly developing industry closely relevant to people's daily lives. Numerous lectures are recorded in form of multimedia data, uploaded to the Internet and made publicly accessible from anywhere in this world. These lectures are generally addressed as e-lectures. In recent year, a new popular form of e-lectures, the Massive Open Online Courses (MOOCs), boosts the growth of online education industry and somehow turns "learning online" into a fashion.
As an e-learning provider, besides to keep improving the quality of e-lecture content, to provide better learning environment for online learners is also a highly important task. This task can be preceded in various ways, and one of them is to enhance and upgrade the learning materials provided: e-lectures could be more than videos. Moreover, this process of enhancement or upgrading should be done automatically, without giving extra burdens to the lecturers or teaching teams, and this is the aim of this thesis.
The first part of this thesis is an integrated framework of multi-lingual subtitles production, which can help online learners penetrate the language barrier. The framework consists of Automatic Speech Recognition (ASR), Sentence Boundary Detection (SBD) and Machine Translation (MT), among which the proposed SBD solution is major technical contribution, building on Deep Neural Network (DNN) and Word Vector (WV) and achieving state-of-the-art performance. Besides, a quantitative evaluation with dozens of volunteers is also introduced to measure how these auto-generated subtitles could actually help in context of e-lectures.
Secondly, a technical solution "TOG" (Tree-Structure Outline Generation) is proposed to extract textual content from the displaying slides recorded in video and re-organize them into a hierarchical lecture outline, which may serve in multiple functions, such like preview, navigation and retrieval. TOG runs adaptively and can be roughly divided into intra-slide and inter-slides phases. Table detection and lecture video segmentation can be implemented as sub- or post-application in these two phases respectively. Evaluation on diverse e-lectures shows that all the outlines, tables and segments achieved are trustworthily accurate.
Based on the subtitles and outlines previously created, lecture videos can be further split into sentence units and slide-based segment units. A lecture highlighting process is further applied on these units, in order to capture and mark the most important parts within the corresponding lecture, just as what people do with a pen when reading paper books. Sentence-level highlighting depends on the acoustic analysis on the audio track, while segment-level highlighting focuses on exploring clues from the statistical information of related transcripts and slide content. Both objective and subjective evaluations prove that the proposed lecture highlighting solution is with decent precision and welcomed by users.
All above enhanced e-lecture materials have been already implemented in actual use or made available for implementation by convenient interfaces.
Contemporary multi-core processors are parallel systems that also provide shared memory for programs running on them. Both the increasing number of cores in so-called many-core systems and the still growing computational power of the cores demand for memory systems that are able to deliver high bandwidths. Caches are essential components to satisfy this requirement. Nevertheless, hardware-based cache coherence in many-core chips faces practical limits to provide both coherence and high memory bandwidths. In addition, a shift away from global coherence can be observed. As a result, alternative architectures and suitable programming models need to be investigated.
This thesis focuses on fast communication for non-cache-coherent many-core architectures. Experiments are conducted on the Single-Chip Cloud Computer (SCC), a non-cache-coherent many-core processor with 48 mesh-connected cores. Although originally designed for message passing, the results of this thesis show that shared memory can be efficiently used for one-sided communication on this kind of architecture. One-sided communication enables data exchanges between processes where the receiver is not required to know the details of the performed communication. In the notion of the Message Passing Interface (MPI) standard, this type of communication allows to access memory of remote processes. In order to support this communication scheme on non-cache-coherent architectures, both an efficient process synchronization and a communication scheme with software-managed cache coherence are designed and investigated.
The process synchronization realizes the concept of the general active target synchronization scheme from the MPI standard. An existing classification of implementation approaches is extended and used to identify an appropriate class for the non-cache-coherent shared memory platform. Based on this classification, existing implementations are surveyed in order to find beneficial concepts, which are then used to design a lightweight synchronization protocol for the SCC that uses shared memory and uncached memory accesses. The proposed scheme is not prone to process skew and also enables direct communication as soon as both communication partners are ready. Experimental results show very good scaling properties and up to five times lower synchronization latency compared to a tuned message-based MPI implementation for the SCC.
For the communication, SCOSCo, a shared memory approach with software-managed cache coherence, is presented. According requirements for the coherence that fulfill MPI's separate memory model are formulated, and a lightweight implementation exploiting SCC hard- and software features is developed. Despite a discovered malfunction in the SCC's memory subsystem, the experimental evaluation of the design reveals up to five times better bandwidths and nearly four times lower latencies in micro-benchmarks compared to the SCC-tuned but message-based MPI library. For application benchmarks, like a parallel 3D fast Fourier transform, the runtime share of communication can be reduced by a factor of up to five. In addition, this thesis postulates beneficial hardware concepts that would support software-managed coherence for one-sided communication on future non-cache-coherent architectures where coherence might be only available in local subdomains but not on a global processor level.
The thesis focuses on the inter-departmental coordination of adaptation and mitigation of demographic change in East Germany. All Eastern German States (Länder) have set up inter-departmental committees (IDCs) that are expected to deliver joint strategies to tackle demographic change. IDCs provide an organizational setting for potential positive coordination, i.e. a joint approach to problem solving that pools and utilizes the expertise of many departments in a constructive manner from the very beginning. Whether they actually achieve positive coordination is contested within the academic debate. This motivates the first research question of this thesis: Do IDCs achieve positive coordination?
Interdepartmental committees and their role in horizontal coordination within the core executive triggered interest among scholars already more than fifty years ago. However, we don’t know much about their actual importance for the inter-departmental preparation of cross-cutting policies. Until now, few studies can be found that analyzes inter-departmental committees in a comparative way trying to identify whether they achieve positive coordination and what factors shape the coordination process and output of IDCs.
Each IDC has a chair organization that is responsible for managing the interactions within the IDCs. The chair organization is important, because it organizes and structures the overall process of coordination in the IDC. Consequently, the chair of an IDC serves as the main boundary-spanner and therefore has remarkable influence by arranging meetings and the work schedule or by distributing internal roles. Interestingly, in the German context we find two organizational approaches: while some states decided to put a line department (e.g. Department of Infrastructure) in charge of managing the IDC, others rely on the State Chancelleries, i.e. the center of government.
This situation allows for comparative research design that can address the role of the State Chancellery in inter-departmental coordination of cross-cutting policies. This is relevant, because the role of the center is crucial when studying coordination within central government. The academic debate on the center of government in the German politico-administrative system is essentially divided into two camps. One camp claims that the center can improve horizontal coordination and steer cross-cutting policy-making more effectively, while the other camp points to limits to central coordination due to departmental autonomy. This debate motivates the second research question of this thesis: Does the State Chancellery as chair organization achieve positive coordination in IDCs?
The center of government and its role in the German politic-administrative system has attracted academic attention already in the 1960s and 1970s. There is a research desiderate regarding the center’s role during the inter-departmental coordination process. There are only few studies that explicitly analyze centers of government and their role in coordination of cross-cutting policies, although some single case studies have been published. This gap in the academic debate will be addressed by the answer to the second research question.
The dependent variable of this study is the chair organization of IDCs. The value of this variable is dichotomous: either an IDC is chaired by a Line department or by a State Chancellery. We are interested whether this variable has an effect on two dependent variables. First, we will analyze the coordination process, i.e. interaction among bureaucrats within the IDC. Second, the focus of this thesis will be on the coordination result, i.e. the demography strategies that are produced by the respective IDCs.
In terms of the methodological approach, this thesis applies a comparative case study design based on a most-similar-systems logic. The German Federalism is quite suitable for such designs. Since the institutional framework largely is the same across all states, individual variables and their effect can be isolated and plausibly analyzed. To further control for potential intervening variables, we will limit our case selection to states located in East Germany, because the demographic situation is most problematic in the Eastern part of Germany, i.e. there is a equal problem pressure. Consequently, we will analyze five cases: Thuringia, Saxony-Anhalt (line department) and Brandenburg, Mecklenburg-Vorpommern and Saxony (State Chancellery).
There is no grand coordination theory that is ready to be applied to our case studies. Therefore, we need to tailor our own approach. Our assumption is that the individual chair organization has an effect on the coordination process and output of IDCs, although all cases are embedded in the same institutional setting, i.e. the German politico-administrative system. Therefore, we need an analytical approach than incorporates institutionalist and agency-based arguments. Therefore, this thesis will utilize Actor-Centered Institutionalism (ACI). Broadly speaking, ACI conceptualizes actors’ behavior as influenced - but not fully determined - by institutions. Since ACI is rather abstract we need to adapt it for the purpose of this thesis. Line Departments and State Chancelleries will be modeled as distinct actors with different action orientations and capabilities to steer the coordination process. However, their action is embedded within the institutional context of governments, which we will conceptualize as being comprised of regulative (formal rules) and normative (social norms) elements.
Introduction: Carbohydrate (CHO) and fat are the main substrates to fuel prolonged endurance exercise, each having its oxidation patterns regulated by several factors such as intensity, duration and mode of the activity, dietary intake pattern, muscle glycogen concentrations, gender and training status. Exercising at intensities where fat oxidation rates are high has been shown to induce metabolic benefits in recreational and health-oriented sportsmen. The exercise intensity (Fatpeak) eliciting peak fat oxidation rates is therefore of particular interest when aiming to prescribe exercise for the purpose of fat oxidation and related metabolic effects. Although running and walking are feasible and popular among the target population, no reliable protocols are available to assess Fatpeak as well as its actual velocity (VPFO) during treadmill ergometry. Moreover, to date, it remains unclear how pre-exercise CHO availability modulates the oxidative regulation of substrates when exercise is conducted at the intensity where the individual anaerobic threshold (IAT) is located (VIAT). That is, a metabolic marker representing the upper border where constant load endurance exercise can be sustained, being commonly used to guide athletic training or in performance diagnostics. The research objectives of the current thesis were therefore, 1) to assess the reliability and day-to-day variability of VPFO and Fatpeak during treadmill ergometry running; 2) to assess the impact of high CHO (HC) vs. low CHO (LC) diets (where on the LC day a combination of low CHO diet and a glycogen depleting exercise was implemented) on the oxidative regulation of CHOs and fat while exercise is conducted at VIAT. Methods: Research objective 1: Sixteen recreational athletes (f=7, m=9; 25 ± 3 y; 1.76 ± 0.09 m; 68.3 ± 13.7 kg; 23.1 ± 2.9 kg/m²) performed 2 different running protocols on 3 different days with standardized nutrition the day before testing. At day 1, peak oxygen uptake (VO2peak) and the velocities at the aerobic threshold (VLT) and respiratory exchange ratio (RER) of 1.00 (VRER) were assessed. At days 2 and 3, subjects ran an identical submaximal incremental test (Fat-peak test) composed of a 10 min warm-up (70% VLT) followed by 5 stages of 6 min with equal increments (stage 1 = VLT, stage 5 = VRER). Breath-by-breath gas exchange data was measured continuously and used to determine fat oxidation rates. A third order polynomial function was used to identify VPFO and subsequently Fatpeak. The reproducibility and variability of variables was verified with an intraclass correlation coefficient (ICC), Pearson’s correlation coefficient, coefficient of variation (CV) and the mean differences (bias) ± 95% limits of agreement (LoA). Research objective 2: Sixteen recreational runners (m=8, f=8; 28 ± 3 y; 1.76 ± 0.09 m; 72 ± 13 kg; 23 ± 2 kg/m²) performed 3 different running protocols, each allocated on a different day. At day 1, a maximal stepwise incremental test was implemented to assess the IAT and VIAT. During days 2 and 3, participants ran a constant-pace bout (30 min) at VIAT that was combined with randomly assigned HC (7g/kg/d) or LC (3g/kg/d) diets for the 24 h before testing. Breath-by-breath gas exchange data was measured continuously and used to determine substrate oxidation. Dietary data and differences in substrate oxidation were analyzed with a paired t-test. A two-way ANOVA tested the diet X gender interaction (α = 0.05). Results: Research objective 1: ICC, Pearson’s correlation and CV for VPFO and Fatpeak were 0.98, 0.97, 5.0%; and 0.90, 0.81, 7.0%, respectively. Bias ± 95% LoA was -0.3 ± 0.9 km/h for VPFO and -2 ± 8% of VO2peak for Fatpeak. Research objective 2: Overall, the IAT and VIAT were 2.74 ± 0.39 mmol/l and 11.1 ± 1.4 km/h, respectively. CHO oxidation was 3.45 ± 0.08 and 2.90 ± 0.07 g/min during HC and LC bouts respectively (P < 0.05). Likewise, fat oxidation was 0.13 ± 0.03 and 0.36 ± 0.03 g/min (P < 0.05). Females had 14% (P < 0.05) and 12% (P > 0.05) greater fat oxidation compared to males during HC and LC bouts, respectively. Conclusions: Research objective 1: In summary, relative and absolute reliability indicators for VPFO and Fatpeak were found to be excellent. The observed LoA may now serve as a basis for future training prescriptions, although fat oxidation rates at prolonged exercise bouts at this intensity still need to be investigated. Research objective 2: Twenty-four hours of high CHO consumption results in concurrent higher CHO oxidation rates and overall utilization, whereas maintaining a low systemic CHO availability significantly increases the contribution of fat to the overall energy metabolism. The observed gender differences underline the necessity of individualized dietary planning before exerting at intensities associated with performance exercise. Ultimately, future research should establish how these findings can be extrapolated to training and competitive situations and with that provide trainers and nutritionists with improved data to derive training prescriptions.
In this work, a sensor system based on thermoresponsive materials is developed by utilizing a modular approach. By synthesizing three different key monomers containing either a carboxyl, alkene or alkyne end group connected with a spacer to the methacrylic polymerizable unit, a flexible copolymerization strategy has been set up with oligo ethylene glycol methacrylates. This allows to tune the lower critical solution temperature (LCST) of the polymers in aqueous media. The molar masses are variable thanks to the excurse taken in polymerization in ionic liquids thus stretching molar masses from 25 to over 1000 kDa. The systems that were shown shown to be effective in aqueous solution could be immobilized on surfaces by copolymerizing photo crosslinkable units. The immobilized systems were formulated to give different layer thicknesses, swelling ratios and mesh sizes depending on the demand of the coupling reaction.
The coupling of detector units or model molecules is approached via reactions of the click chemistry pool, and the reactions are evaluated on their efficiency under those aspects, too. These coupling reactions are followed by surface plasmon resonance spectroscopy (SPR) to judge efficiency. With these tools at hand, Salmonella saccharides could be selectively detected by SPR. Influenza viruses were detected in solution by turbidimetry in solution as well as by a copolymerized solvatochromic dye to track binding via the changes of the polymers’ fluorescence by said binding event. This effect could also be achieved by utilizing the thermoresponsive behavior. Another demonstrator consists of the detection system bound to a quartz surface, thus allowing the virus detection on a solid carrier.
The experiments show the great potential of combining the concepts of thermoresponsive materials and click chemistry to develop technically simple sensors for large biomolecules and viruses.
Nowadays, the need to protect the environment becomes more urgent than ever. In the field of chemistry, this translates to practices such as waste prevention, use of renewable feedstocks, and catalysis; concepts based on the principles of green chemistry. Polymers are an important product in the chemical industry and are also in the focus of these changes. In this thesis, more sustainable approaches to make two classes of polymers, polypeptoids and polyesters, are described.
Polypeptoids or poly(alkyl-N-glycines) are isomers of polypeptides and are biocompatible, as well as degradable under biologically relevant conditions. In addition to that, they can have interesting properties such as lower critical solution temperature (LCST) behavior. They are usually synthesized by the ring opening polymerization (ROP) of N-carboxy anhydrides (NCAs), which are produced with the use of toxic compounds (e.g. phosgene) and which are highly sensitive to humidity. In order to avoid the direct synthesis and isolation of the NCAs, N-phenoxycarbonyl-protected N-substituted glycines are prepared, which can yield the NCAs in situ. The conditions for the NCA synthesis and its direct polymerization are investigated and optimized for the simplest N-substituted glycine, sarcosine. The use of a tertiary amine in less than stoichiometric amounts compared to the N-phenoxycarbonyl--sarcosine seems to accelerate drastically the NCA formation and does not affect the efficiency of the polymerization. In fact, well defined polysarcosines that comply to the monomer to initiator ratio can be produced by this method. This approach was also applied to other N-substituted glycines.
Dihydroxyacetone is a sustainable diol produced from glycerol, and has already been used for the synthesis of polycarbonates. Here, it was used as a comonomer for the synthesis of polyesters. However, the polymerization of dihydroxyacetone presented difficulties, probably due to the insolubility of the macromolecular chains. To circumvent the problem, the dimethyl acetal protected dihydroxyacetone was polymerized with terephthaloyl chloride to yield a soluble polymer. When the carbonyl was recovered after deprotection, the product was insoluble in all solvents, showing that the carbonyl in the main chain hinders the dissolution of the polymers. The solubility issue can be avoided, when a 1:1 mixture of dihydroxyacetone/ ethylene glycol is used to yield a soluble copolyester.
Translating innovation
(2017)
This doctoral thesis studies the process of innovation adoption in public administrations, addressing the research question of how an innovation is translated to a local context. The study empirically explores Design Thinking as a new problem-solving approach introduced by a federal government organisation in Singapore. With a focus on user-centeredness, collaboration and iteration Design Thinking seems to offer a new way to engage recipients and other stakeholders of public services as well as to re-think the policy design process from a user’s point of view. Pioneered in the private sector, early adopters of the methodology include civil services in Australia, Denmark, the United Kingdom, the United States as well as Singapore. Hitherto, there is not much evidence on how and for which purposes Design Thinking is used in the public sector.
For the purpose of this study, innovation adoption is framed in an institutionalist perspective addressing how concepts are translated to local contexts. The study rejects simplistic views of the innovation adoption process, in which an idea diffuses to another setting without adaptation. The translation perspective is fruitful because it captures the multidimensionality and ‘messiness’ of innovation adoption. More specifically, the overall research question addressed in this study is: How has Design Thinking been translated to the local context of the public sector organisation under investigation? And from a theoretical point of view: What can we learn from translation theory about innovation adoption processes?
Moreover, there are only few empirical studies of organisations adopting Design Thinking and most of them focus on private organisations. We know very little about how Design Thinking is embedded in public sector organisations. This study therefore provides further empirical evidence of how Design Thinking is used in a public sector organisation, especially with regards to its application to policy work which has so far been under-researched.
An exploratory single case study approach was chosen to provide an in-depth analysis of the innovation adoption process. Based on a purposive, theory-driven sampling approach, a Singaporean Ministry was selected because it represented an organisational setting in which Design Thinking had been embedded for several years, making it a relevant case with regard to the research question. Following a qualitative research design, 28 semi-structured interviews (45-100 minutes) with employees and managers were conducted. The interview data was triangulated with observations and documents, collected during a field research research stay in Singapore.
The empirical study of innovation adoption in a single organisation focused on the intra-organisational perspective, with the aim to capture the variations of translation that occur during the adoption process. In so doing, this study opened the black box often assumed in implementation studies. Second, this research advances translation studies not only by showing variance, but also by deriving explanatory factors. The main differences in the translation of Design Thinking occurred between service delivery and policy divisions, as well as between the first adopter and the rest of the organisation. For the intra-organisational translation of Design Thinking in the Singaporean Ministry the following five factors played a role: task type, mode of adoption, type of expertise, sequence of adoption, and the adoption of similar practices.
Hintergrund
Für Patienten mit hochgradiger Aortenklappenstenose, die aufgrund ihres Alters oder ihrer Multimorbidität ein hohes Operationsrisiko tragen, konnte mit der kathetergestützten Aortenklappenkorrektur (transcatheter aortic valve implantation, TAVI) eine vielversprechende Alternative zum herzchirurgischen Eingriff etabliert werden. Explizite Daten zur multidisziplinären kardiologischen Rehabilitation nach TAVI liegen bislang nicht vor. Ziel vorliegender Arbeit war, den Effekt der kardiologischen Rehabilitation auf die körperliche Leistungsfähigkeit, den emotionalen Status, die Lebensqualität und die Gebrechlichkeit bei Patienten nach TAVI zu untersuchen sowie Prädiktoren für die Veränderung der körperlichen Leistungsfähigkeit und der Lebensqualität zu identifizieren.
Methodik
Zwischen 10/2013 und 07/2015 wurden 136 Patienten (80,6 ± 5,0 Jahre, 47,8 % Männer) in Anschlussheilbehandlung nach TAVI in drei kardiologischen Rehabilitationskliniken eingeschlossen. Zur Beurteilung des Effekts der kardiologischen Rehabilitation wurden jeweils zu Beginn und Ende der Rehabilitation der Frailty (Gebrechlichkeits)-Index (Score bestehend aus Barthel-Index, Instrumental Activities of Daily Living, Mini Mental State Exam, Mini Nutritional Assessment, Timed Up and Go und subjektiver Mobilitätsverschlechterung), die Lebensqualität im Short-Form 12 (SF-12) sowie die funktionale körperliche Leistungsfähigkeit im 6-Minuten Gehtest (6-minute walk test, 6MWT) und die maximale körperliche Leistungsfähigkeit in der Belastungs-Ergometrie erhoben. Zusätzlich wurden soziodemographische Daten (z. B. Alter und Geschlecht), Komorbiditäten (z. B. chronisch obstruktive Lungenerkrankung, koronare Herzkrankheit und Karzinom), kardiovaskuläre Risikofaktoren und die NYHA-Klasse dokumentiert. Prädiktoren für die Veränderung der körperlichen Leistungsfähigkeit und Lebensqualität wurden mit Kovarianzanalysen angepasst.
Ergebnisse
Die maximale Gehstrecke im 6MWT konnte um 56,3 ± 65,3 m (p < 0,001) und die maximale körperliche Leistungsfähigkeit in der Belastungs-Ergometrie um 8,0 ± 14,9 Watt (p < 0001) gesteigert werden. Weiterhin konnte eine Verbesserung im SF-12 sowohl in der körperlichen Summenskala um 2,5 ± 8,7 Punkte (p = 0,001) als auch in der psychischen Summenskala um 3,4 ± 10,2 Punkte (p = 0,003) erreicht werden. In der multivariaten Analyse waren ein höheres Alter und eine höhere Bildung signifikant mit einer geringeren Zunahme im 6MWT assoziiert, währenddessen eine bessere kognitive Leistungsfähigkeit und Adipositas einen positiven prädiktiven Wert aufwiesen. Eine höhere Selbstständigkeit und ein besserer Ernährungsstatus beeinflussten die Veränderung in der körperlichen Summenskala des SF-12 positiv, währenddessen eine bessere kognitive Leistungsfähigkeit einen Prädiktor für eine geringere Veränderung darstellte. Des Weiteren hatten die jeweiligen Ausgangswerte der körperlichen und psychischen Summenskala im SF-12 einen inversen Einfluss auf die Veränderungen in der gleichen Skala.
Schlussfolgerung
Eine multidisziplinäre kardiologische Rehabilitation kann sowohl die körperliche Leistungs-fähigkeit und Lebensqualität verbessern als auch die Gebrechlichkeit von Patienten nach kathetergestützter Aortenklappenkorrektur verringern. Daraus resultierend gilt es, spezifische Assessments für die kardiologische Rehabilitation zu entwickeln. Weiterhin ist es notwendig, individualisierte Therapieprogramme mit besonderem Augenmerk auf kognitive Funktionen und Ernährung zu initiieren, um die Selbstständigkeit hochbetagter Patienten zu erhalten bzw. wiederherzustellen und um die Pflegebedürftigkeit der Patienten hinauszuzögern.
In dieser Arbeit werden drei Themen im Zusammenhang mit den spektroskopischen Eigenschaften von Cumarin- (Cou) und DBD-Farbstoffen ([1,3]Dioxolo[4,5-f][1,3]benzodioxol) behandelt. Der erste Teil zeigt die grundlegende spektroskopische Charakterisierung von 7-Aminocumarinen und ihre potentielle Anwendung als Fluoreszenzsonde für Fluoreszenzimmunassays. Im zweiten Teil werden mit die photophysikalischen Eigenschaften der Cumarine genutzt um Cou- und DBD-funktionalisierte Oligo-Spiro-Ketal-Stäbe (OSTK) und ihre Eigenschaften als Membransonden zu untersuchen. Der letzte Teil beschäftigt sich mit der Synthese und der Charakterisierung von Cou- und DBD-funktionalisierten Polyprolinen als Referenzsysteme für schwefelfunktionalisierte OSTK-Stäbe und ihrer Kopplung an Goldnanopartikel.
Immunochemische Analysemethoden sind in der klinischen Diagnostik sehr erfolgreich und werden heute auch für die Nahrungsmittelkontrolle und Überwachung von Umweltfragen mit einbezogen. Dadurch sind sie von großem Interesse für weitere Forschungen. Unter den verschiedenen Immunassays zeichnen sich lumineszenzbasierte Formate durch ihre herausragende Sensitivität aus, die dieses Format für zukünftige Anwendungen besonders attraktiv macht. Die Notwendigkeit von Multiparameterdetektionsmöglichkeiten erfordert einen Werkzeugkasten mit Farbstoffen, um die biochemische Reaktion in ein optisch detektierbares Signal umzuwandeln. Hier wird bei einem Multiparameteransatz jeder Analyt durch einen anderen Farbstoff mit einer einzigartigen Emissionsfarbe, die den blauen bis roten Spektralbereich abdecken, oder eine einzigartige Abklingzeit detektiert. Im Falle eines kompetitiven Immunassayformats wäre für jeden der verschiedenen Farbstoffe ein einzelner Antikörper erforderlich. In der vorliegenden Arbeit wird ein leicht modifizierter Ansatz unter Verwendung einer Cumarineinheit, gegen die hochspezifische monoklonale Antikörper (mAb) erzeugt wurden, als grundlegendes Antigen präsentiert. Durch eine Modifikation der Stammcumarineinheit an einer Position des Moleküls, die für die Erkennung durch den Antikörper nicht relevant ist, kann auf den vollen Spektralbereich von blau bis tiefrot zugegriffen werden. In dieser Arbeit wird die photophysikalische Charakterisierung der verschiedenen Cumarinderivate und ihrer entsprechenden Immunkomplexe mit zwei verschiedenen, aber dennoch hochspezifischen, Antikörpern präsentiert. Die Cumarinfarbstoffe und ihre Immunkomplexe wurden durch stationäre und zeitaufgelöste Absorptions- sowie Fluoreszenzemissionsspektroskopie charakterisiert. Darüber hinaus wurden Fluoreszenzdepolarisationsmessungen durchgeführt, um die Daten zu vervollständigen, die die verschiedenen Bindungsmodi der beiden Antikörper betonten. Im Gegensatz zu häufig eingesetzten Nachweissystemen wurde eine massive Fluoreszenzverstärkung bei der Bildung des Antikörper-Farbstoffkomplexes bis zu einem Faktor von 50 gefunden. Wegen der leichten Emissionsfarbenänderung durch das Anpassen der Cumarinsubstitution in der für die Antigenbindung nicht relevanten Position des Elternmoleküls, ist eine Farbstoff-Toolbox vorhanden, die bei der Konstruktion von kompetitiven Multiparameterfluoreszenzverstärkungsimmunassays verwendet werden kann.
Oligo-Spiro-Thio-Ketal-Stäbe werden aufgrund ihres hydrophoben Rückgrats leicht in Doppellipidschichten eingebaut und deshalb als optische Membransonde verwendet. Wegen ihres geringen Durchmessers wird nur eine minimale Störung der Doppellipidschicht verursacht. Durch die Markierung mit Fluoreszenzfarbstoffen sind neuartige Förster-Resonanz-Energietransfersonden mit hoch definierten relativen Orientierungen der Übergangsdipolmomente der Donor- und Akzeptorfarbstoffe zugänglich und macht die Klasse der OSTK-Sonden zu einem leistungsstarken, flexiblen Werkzeugkasten für optische Biosensoranwendungen. Mit Hilfe von stationären und zeitaufgelösten Fluoreszenzexperimenten wurde der Einbau von Cumarin- und DBD markierten OSTK-Stäben in großen unilamellaren Vesikeln untersucht und die Ergebnisse durch Fluoreszenzdepolarisationsmessungen untermauert.
Der letzte Teil dieser Arbeit beschäftigt sich mit der Synthese und Charakterisierung von Cou- und DBD-funktionalisierten Polyprolinen und ihrer Kopplung an Goldnanopartikel. Die farbstoffmarkierten Polyproline konnten erfolgreich hergestellt werden. Es zeigten sich deutlich Einflüsse auf die spektroskopischen Eigenschaften der Farbstoffe durch die Bindung an die Polyprolinhelix. Die Kopplung an die 5 nm großen AuNP konnte erfolgreich durchgeführt werden. Die Erfahrungen, die durch die Kopplung der Polyproline an die AuNP, gewonnen wurde, ist die Basis für eine Einzelmolekül-AFM-FRET-Nanoskopie mit OSTK-Stäben.
Hintergrund: Etablierte Protein- und Nukleinsäure-basierte Methoden für den spezifischen Pathogennachweis sind nur unter standardisierten Laborbedingungen von geschultem Personal durchführbar und daher mit einem hohen Zeit- und Kostenaufwand verbunden. In der Nukleinsäure-basierten Diagnostik kann durch die Einführung der isothermalen Amplifikation eine schnelle und kostengünstige Alternative zur Polymerase-Kettenreaktion (PCR) verwendet werden. Die Loop-mediated isothermal amplification (LAMP) bietet aufgrund der hohen Amplifikationseffizienz vielfältige Detektionsmöglichkeiten, die sowohl für Schnelltest- als auch für Monitoring-Anwendungen geeignet sind.
Ein wesentliches Ziel dieser Arbeit war die Verbesserung der Anwendbarkeit der LAMP und die Entwicklung einer neuen Methode für den einfachen, schnellen und günstigen Nachweis von Pathogenen mittels alternativer DNA- oder Pyrophosphat-abhängiger Detektionsverfahren. Hier wurden zunächst direkte und indirekte Detektionsmethoden untersucht und darauf aufbauend ein Verfahren entwickelt, mit dem neue Metallionen-abhängige Fluoreszenzfarbstoffe für die selektive Detektion von Pyrophosphat in der LAMP und anderen enzymatischen Reaktionen identifiziert werden können. Als Alternative für die DNA-basierte Detektion in der digitalen LAMP sollten die zuvor etablierten Farbstoffe für den Pyrophosphatnachweis in einer Emulsion getestet werden. Abschließend wurde ein neuer Reaktionsmechanismus für die effiziente Generierung hochmolekularer DNA unter isothermalen Bedingungen als Alternative zur LAMP entwickelt.
Ergebnisse: Für den Nachweis RNA- und DNA-basierter Phythopathogene konnte die Echtzeit- und Endpunktdetektion mit verschiedenen Farbstoffen in einem geschlossenen System etabliert werden. Hier wurde Berberin als DNA-interkalierender Fluoreszenzfarbstoff mit vergleichbarer Sensitivität zu SYBR Green und EvaGreen erfolgreich in der LAMP mit Echtzeitdetektion eingesetzt. Ein Vorteil von Berberin gegenüber den anderen Farbstoffen ist die Toleranz der DNA-Polymerase auch bei hohen Farbstoffkonzentrationen. Berberin kann daher auch in der geschlossenen LAMP-Reaktion ohne zusätzliche Anpassung der Reaktionsbedingungen für die Endpunktdetektion verwendet werden. Darüber hinaus konnte Hydroxynaphtholblau (HNB), das für den kolorimetrischen Endpunktnachweis bekannt ist, erstmals auch für die fluorimetrische Detektion der LAMP in Echtzeit eingesetzt werden. Zusätzlich konnten in der Arbeit weitere Metallionen-abhängige Farbstoffe zur indirekten Detektion der LAMP über das Pyrophosphat identifiziert werden. Dafür wurde eine iterative Methode entwickelt, mit der potenzielle Farbstoffe hinsichtlich ihrer Enzymkompatibilität und ihrer spektralen Eigenschaften bei An- oder Abwesenheit von Manganionen selektiert werden können. Mithilfe eines kombinatorischen Screenings im Mikrotiterplattenformat konnte die komplexe Konzentrationsabhängigkeit zwischen den einzelnen Komponenten für einen fluorimetrischen Verdrängungsnachweis untersucht werden. Durch die Visualisierung des Signal-Rausch-Verhältnis’ als Intensitätsmatrix (heatmap) konnten zunächst Alizarinrot S und Tetrazyklin unter simulierten Reaktionsbedingungen selektiert werden. In der anschließenden enzymatischen LAMP-Reaktion konnte insbesondere Alizarinrot S als günstiger, nicht-toxischer und robuster Fluoreszenzfarbstoff identifiziert werden und zeigte eine Pyrophosphat-abhängige Zunahme der Fluoreszenzintensität. Die zuvor etablierten Farbstoffe (HNB, Calcein und Alizarinrot S) konnten anschließend erfolgreich für die indirekte, fluorimetrische Detektion von Pyrophosphat in einer LAMP-optimierten Emulsion eingesetzt werden. Die Stabilität und Homogenität der generierten Emulsion wurde durch den Zusatz des Emulgators Poloxamer 188 verbessert. Durch die fluoreszenzmikroskopische Analyse der Emulsion war eine eindeutige Diskriminierung der positiven und negativen Tröpfchen vor allem bei Einsatz von Calcein und Alizarinrot S möglich. Aufgrund des komplexen Primer-Designs und der hohen Wahrscheinlichkeit unspezifischer Amplifikation in der LAMP wurde eine neue Bst DNA-Polymerase-abhängige isothermale Amplifikationsreaktion entwickelt. Durch die Integration einer spezifischen Linkerstruktur (abasische Stelle oder Hexaethylenglykol) zwischen zwei Primersequenzen konnte ein bifunktioneller Primer die effiziente Regenerierung der Primerbindungsstellen gewährleisten. Der neue Primer induziert nach der spezifischen Hybridisierung auf dem Templat die Rückfaltung zu einer Haarnadelstruktur und blockiert gleichzeitig die Polymeraseaktivität am Gegenstrang, wodurch eine autozyklische Amplifikation trotz konstanter Reaktionstemperatur möglich ist. Die Effizienz der „Hinge-initiated Primer dependent Amplification“ (HIP) konnte abschließend durch die Verkürzung der Distanz zwischen einem modifizierten Hinge-Primer und einem PCR-ähnlichen Primer verbessert werden.
Schlussfolgerung: Die LAMP hat sich aufgrund der hohen Robustheit und Effizienz zu einer leistungsfähigen Alternative für die klassische PCR in der molekularbiologischen Diagnostik entwickelt. Unterschiedliche Detektionsverfahren verbessern die Leistungsfähigkeit der qualitativen und quantitativen LAMP für die Feldanwendungen und für die Diagnostik, da die neuen DNA- und Pyrophosphat-abhängigen Nachweismethoden in einer geschlossenen Reaktion eingesetzt werden können und so eine einfache Pathogendiagnostik ermöglichen. Die gezeigten Methoden können darüber hinaus zu einer Kostensenkung und Zeitersparnis gegenüber den herkömmlichen Methoden beitragen. Ein attraktives Ziel stellt die Weiterentwicklung der HIP für den Pathogennachweis als Alternative zur LAMP dar. Hierbei können die neuen LAMP-Detektionsverfahren ebenfalls Anwendung finden. Die Verwendung von Bst DNA-Polymerase-abhängigen Reaktionen ermöglicht darüber hinaus die Integration einer robusten isothermalen Amplifikation in mikrofluidische Systeme. Durch die Kombination der Probenvorbereitung, Amplifikation und Detektion sind zukünftige Anwendungen mit kurzer Analysezeit und geringem apparativen Aufwand insbesondere in der Pathogendiagnostik möglich.
In this work the human AOX1 was characterized and detailed aspects regarding the expression, the enzyme kinetics and the production of reactive oxygen species (ROS) were investigated. The hAOX1 is a cytosolic enzyme belonging to the molybdenum hydroxylase family. Its catalytically active form is a homodimer with a molecular weight of 300 kDa. Each monomer (150 kDa) consists of three domains: a N-terminal domain (20 kDa) containing two [2Fe-2S] clusters, a 40 kDa intermediate domain containing a flavin adenine dinucleotide (FAD), and a C-terminal domain (85 kDa) containing the substrate binding pocket and the molybdenum cofactor (Moco). The hAOX1 has an emerging role in the metabolism and pharmacokinetics of many drugs, especially aldehydes and N- heterocyclic compounds.
In this study, the hAOX1 was hetereogously expressed in E. coli TP1000 cells, using a new codon optimized gene sequence which improved the expressed protein yield of around 10-fold compared to the previous expression systems for this enzyme. To increase the catalytic activity of hAOX1, an in vitro chemical sulfuration was performed to favor the insertion of the equatorial sulfido ligand at the Moco with consequent increased enzymatic activity of around 10-fold. Steady-state kinetics and inhibition studies were performed using several substrates, electron acceptors and inhibitors. The recombinant hAOX1 showed higher catalytic activity when molecular oxygen was used as electron acceptor. The highest turn over values were obtained with phenanthridine as substrate. Inhibition studies using thioridazine (phenothiazine family), in combination with structural studies performed in the group of Prof. M.J. Romão, Nova Universidade de Lisboa, showed a new inhibition site located in proximity of the dimerization site of hAOX1. The inhibition mode of thioridazine resulted in a noncompetitive inhibition type. Further inhibition studies with loxapine, a thioridazine-related molecule, showed the same type of inhibition. Additional inhibition studies using DCPIP and raloxifene were carried out.
Extensive studies on the FAD active site of the hAOX1 were performed. Twenty new hAOX1 variants were produced and characterized. The hAOX1 variants generated in this work were divided in three groups: I) hAOX1 single nucleotide polymorphisms (SNP) variants; II) XOR- FAD loop hAOX1 variants; III) additional single point hAOX1 variants. The hAOX1 SNP variants G46E, G50D, G346R, R433P, A439E, K1231N showed clear alterations in their catalytic activity, indicating a crucial role of these residues into the FAD active site and in relation to the overall reactivity of hAOX1.
Furthermore, residues of the bovine XOR FAD flexible loop (Q423ASRREDDIAK433) were introduced in the hAOX1. FAD loop hAOX1 variants were produced and characterized for their stability and catalytic activity. Especially the variants hAOX1 N436D/A437D/L438I, N436D/A437D/L438I/I440K and Q434R/N436D/A437D/L438I/I440K showed decreased catalytic activity and stability. hAOX1 wild type and variants were tested for reactivity toward NADH but no reaction was observed.
Additionally, the hAOX1 wild type and variants were tested for the generation of reactive oxygen species (ROS). Interestingly, one of the SNP variants, hAOX1 L438V, showed a high ratio of superoxide prodction. This result showed a critical role for the residue Leu438 in the mechanism of oxygen radicals formation by hAOX1. Subsequently, further hAOX1 variants having the mutated Leu438 residue were produced. The variants hAOX1 L438A, L438F and L438K showed superoxide overproduction of around 85%, 65% and 35% of the total reducing equivalent obtained from the substrate oxidation.
The results of this work show for the first time a characterization of the FAD active site of the hAOX1, revealing the importance of specific residues involved in the generation of ROS and effecting the overall enzymatic activity of hAOX1. The hAOX1 SNP variants presented here indicate that those allelic variations in humans might cause alterations ROS balancing and clearance of drugs in humans.
Mundos comunes
(2017)
A partir de la constatación de una serie de movimientos y diálogos artísticos, correspondientes a las décadas del setenta y ochenta, su tesis doctoral interroga la noción de “lo latinoamericano” en el ámbito del arte y la cultura. La investigación realiza un “viaje recopilatorio” de documentos a través de distintas ciudades europeas que permiten problematizar el lugar, la comunidad y la memoria cultural de lo latinoamericano.
Cellular membranes constantly experience remodeling, as exemplified by morphological changes during endo- and exocytosis. Regulation of membrane morphology is essential for these processes. In this work, we attempt to establish a regulation path based on the use of photoswitches exhibiting conformational changes in model membranes, namely, giant unilamellar vesicles (GUVs). The mechanism of the changes in the GUVs’ morphology caused by isomerization of the photosensitive molecules has been previously explored but still remains elusive. We examine the morphological reshaping of GUVs in the presence of the photoswitch o-tetrafluoroazobenzene (F-azo) and show that the mechanism behind the resulting morphological changes involves both an increase in the membrane area and generation of a positive spontaneous curvature. First, we characterize the partitioning of F-azo in a single-component membrane using both experimental and computational approaches. The partition coefficient calculated from molecular dynamic simulations agrees with experimental data obtained with size-exclusion chromatography. Then, we implement the approach of vesicle electrodeformation in order to assess the increase in the membrane area, which is observed as a result of the conformational change of F-azo. Finally, the local and the effective membrane spontaneous curvatures were estimated from the observed shapes of vesicles exhibiting outward budding. We then extend the application of the F-azo to multicomponent lipid membranes, which exhibit a coexistence of domains in different liquid phases due to a miscibility gap between the lipids. We perform initial experiments to investigate whether F-azo can be employed to modulate the lateral lipid packing and organization. We observe either complete mixing of the domains or the appearing of disordered domains within the domains of more ordered phase. The type of behavior observed in response to the photoisomerization of F-azo was dependent on the used lipid composition. We believe that the findings introduced here will have an impact in understanding and controlling both lipid phase modulation and regulation of the membrane morphology in membrane systems.
Steep mountain channels are an important component of the fluvial system. On geological timescales, they shape mountain belts and counteract tectonic uplift by erosion. Their channels are strongly coupled to hillslopes and they are often the main source of sediment transported downstream to low-gradient rivers and to alluvial fans, where commonly settlements in mountainous areas are located. Hence, mountain streams are the cause for one of the main natural hazards in these regions. Due to climate change and a pronounced populating of mountainous regions the attention given to this threat is even growing. Although quantitative studies on sediment transport have significantly advanced our knowledge on measuring and calibration techniques we still lack studies of the processes within mountain catchments. Studies examining the mechanisms of energy and mass exchange on small temporal and spatial scales in steep streams remain sparse in comparison to low-gradient alluvial channels.
In the beginning of this doctoral project, a vast amount of experience and knowledge of a steep stream in the Swiss Prealps had to be consolidated in order to shape the principal aim of this research effort. It became obvious, that observations from within the catchment are underrepresented in comparison to experiments performed at the catchment’s outlet measuring fluxes and the effects of the transported material. To counteract this imbalance, an examination of mass fluxes within the catchment on the process scale was intended. Hence, this thesis is heavily based on direct field observations, which are generally rare in these environments in quantity and quality. The first objective was to investigate the coupling of the channel with surrounding hillslopes, the major sources of sediment. This research, which involved the monitoring of the channel and adjacent hillslopes, revealed that alluvial channel steps play a key role in coupling of channel and hillslopes. The observations showed that hillslope stability is strongly associated with the step presence and an understanding of step morphology and stability is therefore crucial in understanding sediment mobilization. This finding refined the way we think about the sediment dynamics in steep channels and motivated continued research of the step dynamics. However, soon it became obvious that the technological basis for developing field tests and analyzing the high resolution geometry measured in the field was not available. Moreover, for many geometrical quantities in mountain channels definitions and a clear scientific standard was not available. For example, these streams are characterized by a high spatial variability of the channel banks, preventing straightforward calculations of the channel width without a defined reference. Thus, the second and inevitable part of this thesis became the development and evaluation of scientific tools in order to investigate the geometrical content of the study reach thoroughly. The developed framework allowed the derivation of various metrics of step and channel geometry which facilitated research on the a large data set of observations of channel steps. In the third part, innovative, physically-based metrics have been developed and compared to current knowledge on step formation, suggested in the literature. With this analyses it could be demonstrated that the formation of channel steps follow a wide range of hydraulic controls. Due to the wide range of tested parameters channel steps observed in a natural stream were attributed to different mechanisms of step formation, including those based on jamming and those based on key-stones. This study extended our knowledge on step formation in a steep stream and harmonized different, often time seen as competing, processes of step formation. This study was based on observations collected at one point in time. In the fourth part of this project, the findings of the snap-shot observations were extended in the temporal dimension and the derived concepts have been utilized to investigate reach-scale step patterns in response to large, exceptional flood events. The preliminary results of this work based on the long-term analyses of 7 years of long profile surveys showed that the previously observed channel-hillslope mechanism is the responsible for the short-term response of step formation.
The findings of the long-term analyses of step patterns drew a bow to the initial observations of a channel-hillslope system which allowed to join the dots in the dynamics of steep stream. Thus, in this thesis a broad approach has been chosen to gain insights into the complex system of steep mountain rivers. The effort includes in situ field observations (article I), the development of quantitative scientific tools (article II), the reach-scale analyses of step-pool morphology (article III) and its temporal evolution (article IV). With this work our view on the processes within the catchment has been advanced towards a better mechanistic understanding of these fluvial system relevant to improve applied scientific work.
Lignin valorization
(2017)
The topic of this project is the use of lignin as alternative source of aromatic building blocks and oligomers to fossil feedstocks. Lignin is known as the most abundant aromatic polymer in nature and is isolated from the lignocellulosic component of plants by different possible extraction treatments. Both the biomass source and the extraction method affect the structure of the isolated lignin, therefore influencing its further application. Lignin was extracted from beech wood by two different hydrothermal alkaline treatments, which use NaOH and Ba(OH)2 as base and by an acid-catalyzed organosolv process. Moreover, lignin was isolated from bamboo, beech wood and coconut by soda treatment of the biomasses. A comparison of the structural features of such isolated lignins was performed through the use of a wide range of analytical methods. Alkaline lignins resulted in a better candidate as carbon precursor and macromonomers for the synthesis of polymer than organosolv lignin. In fact, alkaline lignins showed higher residual mass after carbonization and higher content of the reactive hydroxy functionalities. In contrast, the lignin source turned out to slightly affect the lignin hydroxyl content.
One of the most common lignin modifications is its deconstruction to obtain aromatic molecules, which can be used as starting materials for the synthesis of fine chemicals. Lignin deconstruction leads to a complex mixture of aromatic molecules. A gas chromatographic analytical method was developed to characterize the mixture of products obtained by lignin deconstruction via heterogeneous catalytic hydrogenolysis. The analytical protocol allowed the quantification of three main groups of molecules by means of calibration curves, internal standard and a preliminary silylation step of the sample. The analytical method was used to study the influence of the hydrogenolysis catalyst, temperature and system (flow and batch reactor) on the yield and selectivity of the aromatic compounds.
Lignin extracted from beech wood by a hydrothermal process using Ba(OH)2 as base, was functionalized by aromatic nitration in order to add nitrogen functionalities. The final goal was the synthesis of a nitrogen doped carbon. Nitrated lignin was reduced to the amino form in order to compare the influence of different nitrogen functionalities on the porosity of the final carbon. The carbons were obtained by ionothermal treatment of the precursors in the presence of the eutectic salt mixture KCl/ZnCl2 Such synthesized carbons showed micro-, macro- and mesoporosity and were tested for their electrocatalytic activity towards the oxygen reduction reaction. Mesoporous carbon derived from nitro lignin displayed the highest electrocatalytic activity.
Lignins isolated from coconut, beech wood and bamboo were used as macromonomers for the synthesis of biobased polyesters. A condensation reaction was performed between lignin and a hyper branched poly(ester-amine), previously obtained by condensation of triethanolamine and adipic acid. The influence of the lignin source and content on the thermochemical and mechanical properties of the final material was investigated. The prepolymer showed adhesive properties towards aluminum and its shear strength was therefore measured. The gluing properties of such synthesized glues turned out to be independent from the lignin source but affected by the amount of lignin in the final material.
This work shows that, although still at a laboratory scale, the valorization of lignin can overcome the critical issues of lignin´s structure variability and complexity.
This is a cumulative dissertation comprising three original studies (one published, one in revision, one submitted; Effective December 2017) investigating how reptile species in arid Australia respond to various climatic parameters at different spatial scales and analysing the two potential main underlying mechanisms: thermoregulatory behaviour and species interactions. This dissertation combines extensive individual-based field data across trophic levels, selected field experiments, statistical analyses, and predictive modelling techniques. Mechanisms and processes detected in this dissertation can now be used to predict potential future changes in the community of arid-zone lizards. This knowledge will help improving our fundamental understanding of the consequences of global change and thereby prevent biodiversity loss in a vulnerable ecosystem.
In the wake of 21st century, humanity witnessed a phenomenal raise of urban agglomerations as powerhouses for innovation and socioeconomic growth. Driving much of national (and in few instances even global) economy, such a gargantuan raise of cities is also accompanied by subsequent increase in energy, resource consumption and waste generation. Much of anthropogenic transformation of Earth's environment in terms of environmental pollution at local level to planetary scale in the form of climate change is currently taking place in cities. Projected to be crucibles for entire humanity by the end of this century, the ultimate fate of humanity predominantly lies in the hands of technological innovation, urbanites' attitudes towards energy/resource consumption and development pathways undertaken by current and future cities. Considering the unparalleled energy, resource consumption and emissions currently attributed to global cities, this thesis addresses these issues from an efficiency point of view. More specifically, this thesis addresses the influence of population size, density, economic geography and technology in improving urban greenhouse gas (GHG) emission efficiency and identifies the factors leading to improved eco-efficiency in cities. In order to investigate the in uence of these factors in improving emission and resource efficiency in cities, a multitude of freely available datasets were coupled with some novel methodologies and analytical approaches in this thesis.
Merging the well-established Kaya Identity to the recently developed urban scaling laws, an Urban Kaya Relation is developed to identify whether large cities are more emission efficient and the intrinsic factors leading to such (in)efficiency. Applying Urban Kaya Relation to a global dataset of 61 cities in 12 countries, this thesis identifed that large cities in developed regions of the world will bring emission efficiency gains because of the better technologies implemented in these cities to produce and utilize energy consumption while the opposite is the case for cities in developing regions. Large cities in developing countries are less efficient mainly because of their affluence and lack of efficient technologies. Apart from the in uence of population size on emission efficiency, this thesis identified the crucial role played by population density in improving building and on-road transport sector related emission efficiency in cities. This is achieved by applying the City Clustering Algorithm (CCA) on two different gridded land use datasets and a standard emission inventory to attribute these sectoral emissions to all inhabited settlements in the USA. Results show that doubling the population density would entail a reduction in the total CO2 emissions in buildings and on-road sectors typically by at least 42 %. Irrespective of their population size and density, cities are often blamed for their intensive resource consumption that threatens not only local but also global sustainability. This thesis merged the concept of urban metabolism with benchmarking and identified cities which are eco-efficient. These cities enable better socioeconomic conditions while being less burden to the environment. Three environmental burden indicators (annual average NO2 concentration, per capita waste generation and water consumption) and two socioeconomic indicators (GDP per capita and employment ratio) for 88 most populous European cities are considered in this study. Using two different non-parametric ranking methods namely regression residual ranking and Data Envelopment Analysis (DEA), eco-efficient cities and their determining factors are identified. This in-depth analysis revealed that mature cities with well-established economic structures such as Munich, Stockholm and Oslo are eco-efficient. Further, correlations between objective eco-efficiency ranking with each of the indicator rankings and the ranking of urbanites' subjective perception about quality of life are analyzed. This analysis revealed that urbanites' perception about quality of life is not merely confined to the socioeconomic well-being but rather to their combination with lower environmental burden.
In summary, the findings of this dissertation has three general conclusions for improving emission and ecological efficiency in cities. Firstly, large cities in emerging nations face a huge challenge with respect to improving their emission efficiency. The task in front of these cities is threefold: (1) deploying efficient technologies for the generation of electricity and improvement of public transportation to unlock their leap frogging potential, (2) addressing the issue of energy poverty and (3) ensuring that these cities do not develop similar energy consumption patterns with infrastructure lock-in behavior similar to those of cities in developed regions. Secondly, the on-going urban sprawl as a global phenomenon will decrease the emission efficiency within the building and transportation sector. Therefore, local policy makers should identify adequate fiscal and land use policies to curb urban sprawl. Lastly, since mature cities with well-established economic structures are more eco-efficient and urbanites' perception re ects its combination with decreasing environmental burden; there is a need to adopt and implement strategies which enable socioeconomic growth in cities whilst decreasing their environment burden.
Observational and computational extragalactic astrophysics are two fields of research that study a similar subject from different perspectives. Observational extragalactic astrophysics aims, by recovering the spectral energy distribution of galaxies at different wavelengths, to reliably measure their properties at different cosmic times and in a large variety of environments. Analyzing the light collected by the instruments, observers try to disentangle the different processes occurring in galaxies at the scales of galactic physics, as well as the effect of larger scale processes such as mergers and accretion, in order to obtain a consistent picture of galaxy formation and evolution. On the other hand, hydrodynamical simulations of galaxy formation in cosmological context are able to follow the evolution of a galaxy along cosmic time, taking into account both external processes such as mergers, interactions and accretion, and internal mechanisms such as feedback from Supernovae and Active Galactic Nuclei. Due to the great advances in both fields of research, we have nowadays available spectral and photometric information for a large number of galaxies in the Universe at different cosmic times, which has in turn provided important knowledge about the evolution of the Universe; at the same time, we are able to realistically simulate galaxy formation and evolution in large volumes of the Universe, taking into account the most relevant physical processes occurring in galaxies.
As these two approaches are intrinsically different in their methodology and in the information they provide, the connection between simulations and observations is still not fully established, although simulations are often used in galaxies' studies to interpret observations and assess the effect of the different processes acting on galaxies on the observable properties, and simulators usually test the physical recipes implemented in their hydrodynamical codes through the comparison with observations. In this dissertation we aim to better connect the observational and computational approaches in the study of galaxy formation and evolution, using the methods and results of one field to test and validate the methods and results of the other.
In a first work we study the biases and systematics in the derivation of the galaxy properties in observations. We post-process hydrodynamical cosmological simulations of galaxy formation to calculate the galaxies' Spectral Energy Distributions (SEDs) using different approaches, including radiative transfer techniques. Comparing the direct results of the simulations with the quantities obtained applying observational techniques to these synthetic SEDs, we are able to make an analysis of the biases intrinsic in the observational algorithms, and quantify their accuracy in recovering the galaxies' properties, as well as estimating the uncertainties affecting a comparison between simulations and observations when different approaches to obtain the observables are followed. Our results show that for some quantities such as the stellar ages, metallicities and gas oxygen abundances large differences can appear, depending on the technique applied in the derivation.
In a second work we compare a set of fifteen galaxies similar in mass to the Milky Way and with a quiet merger history in the recent past (hence expected to have properties close to spiral galaxies), simulated in a cosmological context, with data from the Sloan Digital Sky Survey (SDSS). We use techniques to obtain the observables as similar as possible to the ones applied in SDSS, with the aim of making an unbiased comparison between our set of hydrodynamical simulations and SDSS observations. We quantify the differences in the physical properties when these are obtained directly from the simulations without post-processing, or mimicking the SDSS observational techniques. We fit linear relations between the values derived directly from the simulations and following SDSS observational procedures, which in most of the cases have relatively high correlation, that can be easily used to more reliably compare simulations with SDSS data. When mimicking SDSS techniques, these simulated galaxies are photometrically similar to galaxies in the SDSS blue sequence/green valley, but have in general older ages, lower SFRs and metallicities compared to the majority of the spirals in the observational dataset.
In a third work, we post-process hydrodynamical simulations of galaxies with radiative transfer techniques, to generate synthetic data that mimic the properties of the CALIFA Integral Field Spectroscopy (IFS) survey. We reproduce the main characteristics of the CALIFA observations in terms of field of view and spaxel physical size, data format, point spread functions and detector noise. This 3-dimensional dataset is suited to be analyzed by the same algorithms applied to the CALIFA dataset, and can be used as a tool to test the ability of the observational algorithms in recovering the properties of the CALIFA galaxies. To this purpose, we also generate the resolved maps of the simulations' properties, calculated directly from the hydrodynamical snapshots, or from the simulated spectra prior to the addition of the noise.
Our work shows that a reliable connection between the models and the data is of crucial importance both to judge the output of galaxy formation codes and to accurately test the observational algorithms used in the analysis of galaxy surveys' data. A correct interpretation of observations will be particularly important in the future, in light of the several ongoing and planned large galaxy surveys that will provide the community with large datasets of properties of galaxies (often spatially-resolved) at different cosmic times, allowing to study galaxy formation physics at a higher level of detail than ever before. We have shown that neglecting the observational biases in the comparison between simulations and an observational dataset may move the simulations to different regions in the planes of the observables, strongly affecting the assessment of the correctness of the sub-resolution physical models implemented in galaxy formation codes, as well as the interpretation of given observational results using simulations.
Nanolenses are linear chains of differently-sized metal nanoparticles, which can theoretically provide extremely high field enhancements. The complex structure renders their synthesis challenging and has hampered closer analyses so far. Here, the technique of DNA origami was used to self-assemble DNA-coated 10 nm, 20 nm, and 60 nm gold or silver nanoparticles into gold or silver nanolenses. Three different geometrical arrangements of gold nanolenses were assembled, and for each of the three, sets of single gold nanolenses were investigated in detail by atomic force microscopy, scanning electron microscopy, dark-field scattering and Raman spectroscopy. The surface-enhanced Raman scattering (SERS) capabilities of the single nanolenses were assessed by labelling the 10 nm gold nanoparticle selectively with dye molecules. The experimental data was complemented by finite-difference time-domain simulations. For those gold nanolenses which showed the strongest field enhancement, SERS signals from the two different internal gaps were compared by selectively placing probe dyes on the 20 nm or 60 nm gold particles. The highest enhancement was found for the gap between the 20 nm and 10 nm nanoparticle, which is indicative of a cascaded field enhancement. The protein streptavidin was labelled with alkyne groups and served as a biological model analyte, bound between the 20 nm and 10 nm particle of silver nanolenses. Thereby, a SERS signal from a single streptavidin could be detected. Background peaks observed in SERS measurements on single silver nanolenses could be attributed to amorphous carbon. It was shown that the amorphous carbon is generated in situ.
Magnetische Eisenoxidnanopartikel werden bereits seit geraumer Zeit erfolgreich als MRT-Kontrastmittel in der klinischen Bildgebung eingesetzt. Durch Optimierung der magnetischen Eigenschaften der Nanopartikel kann die Aussagekraft von MR-Aufnahmen verbessert und somit der diagnostische Wert einer MR-Anwendung weiter erhöht werden. Neben der Verbesserung bestehender Verfahren wird die bildgebende Diagnostik ebenso durch die Entwicklung neuer Verfahren, wie dem Magnetic Particle Imaging, vorangetrieben. Da hierbei das Messsignal von den magnetischen Nanopartikeln selbst erzeugt wird, birgt das MPI einen enormen Vorteil hinsichtlich der Sensitivität bei gleichzeitig hoher zeitlicher und räumlicher Auflösung. Da es aktuell jedoch keinen kommerziell vertriebenen in vivo-tauglichen MPI-Tracer gibt, besteht ein dringender Bedarf an geeigneten innovativen Tracermaterialien. Daraus resultierte die Motivation dieser Arbeit biokompatible und superparamagnetische Eisenoxidnanopartikel für den Einsatz als in vivo-Diagnostikum insbesondere im Magnetic Particle Imaging zu entwickeln. Auch wenn der Fokus auf der Tracerentwicklung für das MPI lag, wurde ebenso die MR-Performance bewertet, da geeignete Partikel somit alternativ oder zusätzlich als MR-Kontrastmittel mit verbesserten Kontrasteigenschaften eingesetzt werden könnten.
Die Synthese der Eisenoxidnanopartikel erfolgte über die partielle Oxidation von gefälltem Eisen(II)-hydroxid und Green Rust sowie eine diffusionskontrollierte Kopräzipitation in einem Hydrogel.
Mit der partiellen Oxidation von Eisen(II)-hydroxid und Green Rust konnten erfolgreich biokompatible und über lange Zeit stabile Eisenoxidnanopartikel synthetisiert werden. Zudem wurden geeignete Methoden zur Formulierung und Sterilisierung etabliert, wodurch zahlreiche Voraussetzungen für eine Anwendung als in vivo-Diagnostikum geschaffen wurden. Weiterhin ist auf Grundlage der MPS-Performance eine hervorragende Eignung dieser Partikel als MPI-Tracer zu erwarten, wodurch die Weiterentwicklung der MPI-Technologie maßgeblich vorangetrieben werden könnte. Die Bestimmung der NMR-Relaxivitäten sowie ein initialer in vivo-Versuch zeigten zudem das große Potential der formulierten Nanopartikelsuspensionen als MRT-Kontrastmittel. Die Modifizierung der Partikeloberfläche ermöglicht ferner die Herstellung zielgerichteter Nanopartikel sowie die Markierung von Zellen, wodurch das mögliche Anwendungsspektrum maßgeblich erweitert wurde.
Im zweiten Teil wurden Partikel durch eine diffusionskontrollierte Kopräzipitation im Hydrogel, wobei es sich um eine bioinspirierte Modifikation der klassischen Kopräzipitation handelt, synthetisiert, wodurch Partikel mit einer durchschnittlichen Kristallitgröße von 24 nm generiert werden konnten. Die Bestimmung der MPS- und MR-Performance elektrostatisch stabilisierter Partikel ergab vielversprechende Resultate. In Vorbereitung auf die Entwicklung eines in vivo-Diagnostikums wurden die Partikel anschließend erfolgreich sterisch stabilisiert, wodurch der kolloidale Zustand in MilliQ-Wasser über lange Zeit aufrechterhalten werden konnte. Durch Zentrifugation konnten die Partikel zudem erfolgreich in verschiedene Größenfraktionen aufgetrennt werden. Dies ermöglichte die Bestimmung der idealen Aggregatgröße dieses Partikelsystems in Bezug auf die MPS-Performance.
The existence of diverse and active microbial ecosystems in the deep subsurface – a biosphere that was originally considered devoid of life – was discovered in multiple microbiological studies. However, most of the studies are restricted to marine ecosystems, while our knowledge about the microbial communities in the deep subsurface of lake systems and their potentials to adapt to changing environmental conditions is still fragmentary. This doctoral thesis aims to build up a unique data basis for providing the first detailed high-throughput characterization of the deep biosphere of lacustrine sediments and to emphasize how important it is to differentiate between the living and the dead microbial community in deep biosphere studies.
In this thesis, up to 3.6 Ma old sediments (up to 317 m deep) of the El’gygytgyn Crater Lake were examined, which represents the oldest terrestrial climate record of the Arctic. Combining next generation sequencing with detailed geochemical characteristics and other environmental parameters, the microbial community composition was analyzed in regard to changing climatic conditions within the last 3.6 Ma to 1.0 Ma (Pliocene and Pleistocene). DNA from all investigated sediments was successfully extracted and a surprisingly diverse (6,910 OTUs) and abundant microbial community in the El’gygytgyn deep sediments were revealed. The bacterial abundance (10³-10⁶ 16S rRNA copies g⁻¹ sediment) was up to two orders of magnitudes higher than the archaeal abundance (10¹-10⁵) and fluctuates with the Pleistocene glacial/interglacial cyclicality. Interestingly, a strong increase in the microbial diversity with depth was observed (approximately 2.5 times higher diversity in Pliocene sediments compared to Pleistocene sediments). The increase in diversity with depth in the Lake El’gygytgyn is most probably caused by higher sedimentary temperatures towards the deep sediment layers as well as an enhanced temperature-induced intra-lake bioproductivity and higher input of allochthonous organic-rich material during Pliocene climatic conditions. Moreover, the microbial richness parameters follow the general trends of the paleoclimatic parameters, such as the paleo-temperature and paleo-precipitation. The most abundant bacterial representatives in the El’gygytgyn deep biosphere are affiliated with the phyla Proteobacteria, Actinobacteria, Bacteroidetes, and Acidobacteria, which are also commonly distributed in the surrounding permafrost habitats. The predominated taxon was the halotolerant genus Halomonas (in average 60% of the total reads per sample).
Additionally, this doctoral thesis focuses on the live/dead differentiation of microbes in cultures and environmental samples. While established methods (e.g., fluorescence in situ hybridization, RNA analyses) are not applicable to the challenging El’gygytgyn sediments, two newer methods were adapted to distinguish between DNA from live cells and free (extracellular, dead) DNA: the propidium monoazide (PMA) treatment and the cell separation adapted for low amounts of DNA. The applicability of the DNA-intercalating dye PMA was successfully evaluated to mask free DNA of different cultures of methanogenic archaea, which play a major role in the global carbon cycle. Moreover, an optimal procedure to simultaneously treat bacteria and archaea was developed using 130 µM PMA and 5 min of photo-activation with blue LED light, which is also applicable on sandy environmental samples with a particle load of ≤ 200 mg mL⁻¹. It was demonstrated that the soil texture has a strong influence on the PMA treatment in particle-rich samples and that in particular silt and clay-rich samples (e.g., El’gygytgyn sediments) lead to an insufficient shielding of free DNA by PMA. Therefore, a cell separation protocol was used to distinguish between DNA from live cells (intracellular DNA) and extracellular DNA in the El’gygytgyn sediments. While comparing these two DNA pools with a total DNA pool extracted with a commercial kit, significant differences in the microbial composition of all three pools (mean distance of relative abundance: 24.1%, mean distance of OTUs: 84.0%) was discovered. In particular, the total DNA pool covers significantly fewer taxa than the cell-separated DNA pools and only inadequately represents the living community. Moreover, individual redundancy analyses revealed that the microbial community of the intra- and extracellular DNA pool are driven by different environmental factors. The living community is mainly influenced by life-dependent parameters (e.g., sedimentary matrix, water availability), while the extracellular DNA is dependent on the biogenic silica content. The different community-shaping parameters and the fact, that a redundancy analysis of the total DNA pool explains significantly less variance of the microbial community, indicate that the total DNA represents a mixture of signals of the live and dead microbial community.
This work provides the first fundamental data basis of the diversity and distribution of microbial deep biosphere communities of a lake system over several million years. Moreover, it demonstrates the substantial importance of extracellular DNA in old sediments. These findings may strongly influence future environmental community analyses, where applications of live/dead differentiation avoid incorrect interpretations due to a failed extraction of the living microbial community or an overestimation of the past community diversity in the course of total DNA extraction approaches.
Detection and Kirchhoff-type migration of seismic events by use of a new characteristic function
(2017)
The classical method of seismic event localization is based on the picking of body wave arrivals, ray tracing and inversion of travel time data. Travel time picks with small uncertainties are required to produce reliable and accurate results with this kind of source localization. Hence recordings, with a low Signal-to-Noise Ratio (SNR) cannot be used in a travel time based inversion. Low SNR can be related with weak signals from distant and/or low magnitude sources as well as with a high level of ambient noise. Diffraction stacking is considered as an alternative seismic event localization method that enables also the processing of low SNR recordings by mean of stacking the amplitudes of seismograms along a travel time function. The location of seismic event and its origin time are determined based on the highest stacked amplitudes (coherency) of the image function. The method promotes an automatic processing since it does not need travel time picks as input data.
However, applying diffraction stacking may require longer computation times if only limited computer resources are used. Furthermore, a simple diffraction stacking of recorded amplitudes could possibly fail to locate the seismic sources if the focal mechanism leads to complex radiation patterns which typically holds for both natural and induced seismicity.
In my PhD project, I have developed a new work flow for the localization of seismic events which is based on a diffraction stacking approach. A parallelized code was implemented for the calculation of travel time tables and for the determination of an image function to reduce computation time. In order to address the effects from complex source radiation patterns, I also suggest to compute diffraction stacking from a characteristic function (CF) instead of stacking the original wave form data. A new CF, which is called in the following mAIC (modified from Akaike Information Criterion) is proposed. I demonstrate that, the performance of the mAIC does not depend on the chosen length of the analyzed time window and that both P- and S-wave onsets can be detected accurately. To avoid cross-talk between P- and S-waves due to inaccurate velocity models, I separate the P- and S-waves from the mAIC function by making use of polarization attributes. Then, eventually the final image function is represented by the largest eigenvalue as a result of the covariance analysis between P- and S-image functions. Before applying diffraction stacking, I also apply seismogram denoising by using Otsu thresholding in the time-frequency domain.
Results from synthetic experiments show that the proposed diffraction stacking provides reliable results even from seismograms with low SNR=1. Tests with different presentations of the synthetic seismograms (displacement, velocity, and acceleration) shown that, acceleration seismograms deliver better results in case of high SNR, whereas displacement seismograms provide more accurate results in case of low SNR recordings. In another test, different measures (maximum amplitude, other statistical parameters) were used to determine the source location in the final image function. I found that the statistical approach is the preferred method particularly for low SNR.
The work flow of my diffraction stacking method was finally applied to local earthquake data from Sumatra, Indonesia. Recordings from a temporary network of 42 stations deployed for 9 months around the Tarutung pull-apart Basin were analyzed. The seismic event locations resulting from the diffraction stacking method align along a segment of the Sumatran Fault. A more complex distribution of seismicity is imaged within and around the Tarutung Basin. Two lineaments striking N-S were found in the middle of the Tarutung Basin which support independent results from structural geology. These features are interpreted as opening fractures due to local extension. A cluster of seismic events repeatedly occurred in short time which might be related to fluid drainage since two hot springs are observed at the surface near to this cluster.
In der vorliegenden Arbeit konnte gezeigt werden, dass die beiden verwendeten Amphiphile mit Cholesterol als hydrophoben Block, gute Template für die Mineralisation von Calciumphosphat an der Wasser/Luft-Grenzfläche sind. Mittels Infrarot-Reflexions-Absorptions-Spektroskopie (IRRAS), Röntgenphotoelektronenspektroskopie (XPS), Energie dispersiver Röntgenspektroskopie (EDXS), Elektronenbeugung (SAED) und hochauflösende Transmissionselektronenmikroskopie (HRTEM) konnte die erfolgreiche Mineralisation von Calciumphosphat für beide Amphiphile an der Wasser/Luft-Grenzfläche nachgewiesen werden. Es konnte auch gezeigt werden, dass das Phasenverhalten der beiden Amphiphile und die bei der Mineralisation von Calciumphosphat gebildeten Kristallphasen nicht identisch sind. Beide Amphiphile üben demnach einen unterschiedlichen Einfluss auf den Mineralisationsverlauf aus.
Beim CHOL-HEM konnte sowohl nach 3 h als auch nach 5 h Octacalciumphosphat (OCP) als einzige Kristallphase mittels XPS, SAED, HRTEM und EDXS nachgewiesen werden. Das A-CHOL hingegen zeigte bei der Mineralisation von Calciumphosphat nach 1 h zunächst eine nicht eindeutig identifizierbare Vorläuferphase aus amorphen Calciumphosphat, Brushit (DCPD) oder OCP. Diese wandelte sich dann nach 3 h und 5 h in ein Gemisch, bestehend aus OCP und ein wenig Hydroxylapatit (HAP) um.
Die Schlussfolgerung daraus ist, dass das CHOL-HEM in der Lage ist, dass während der Mineralisation entstandene OCP zu stabilisieren. Dies geschieht vermutlich durch die Adsorption des Amphiphils bevorzugt an der OCP Oberfläche in [100] Orientierung. Dadurch wird die Spaltung entlang der c-Achse unterdrückt und die Hydrolyse zum HAP verhindert.
Das A-CHOL ist hingegen sterisch anspruchsvoller und kann wahrscheinlich aufgrund seiner Größe nicht so gut an der OCP Kristalloberfläche adsorbieren verglichen zum CHOL HEM. Das CHOL-HEM kann also die Hydrolyse von OCP zu HAP besser unterdrücken als das A-CHOL. Da jedoch auch beim A-CHOL nach einer Mineralisationszeit von 5 h nur wenig HAP zu finden ist, wäre auch hier ein Stabilisierungseffekt der OCP Kristalle möglich. Um eine genaue Aussage darüber treffen zu können, sind jedoch zusätzliche Kontrollexperimente notwendig. Es wäre zum einen denkbar, die Mineralisationsexperimente über einen längeren Zeitraum durchzuführen. Diese könnten zeigen, ob das CHOL-HEM die Hydrolyse vom OCP zum HAP komplett unterdrückt. Außerdem könnte nachgewiesen werden, ob beim A-CHOL das OCP weiter zum HAP umgesetzt wird oder ob ein Gemisch beider Kristallphasen erhalten bleibt.
Um die Mineralisation an der Wasser/Luft-Grenzfläche mit der Mineralisation in Bulklösung zu vergleichen, wurden zusätzlich Mineralisationsexperimente in Bulklösung durchgeführt. Dazu wurden Nitrilotriessigsäure (NTA) und Ethylendiamintetraessigsäure (EDTA) als Mineralisationsadditive verwendet, da NTA unter anderem der Struktur der hydrophilen Kopfgruppe des A-CHOLs ähnelt. Es konnte gezeigt werden, dass ein Vergleich der Mineralisation an der Grenzfläche mit der Mineralisation in Bulklösung nicht ohne weiteres möglich ist. Bei der Mineralisation in Bulklösung wird bei tiefen pH-Werten DCPD und bei höheren pH-Werten HAP gebildet. Diese wurde mittels Röntgenpulverdiffraktometrie Messungen nachgewiesen und durch Infrarotspektroskopie bekräftigt. Die Bildung von OCP wie an der Wasser/Luft-Grenzfläche konnte nicht beobachtet werden.
Es konnte auch gezeigt werden, dass beide Additive NTA und EDTA einen unterschiedlichen Einfluss auf den Verlauf der Mineralisation nehmen. So unterscheiden sich zum einen die Morphologien des gebildeten DCPDs und zum anderen wurde beispielsweise in Anwesenheit von 10 und 15 mM NTA neben DCPD auch HAP bei einem Ausgangs-pH-Wert von 7 nachgewiesen.
Da unser Augenmerk speziell auf der Mineralisation von Calciumphosphat an der Wasser/Luft-Grenzfläche liegt, könnten Folgeexperimente wie beispielsweise GIXD Messungen durchgeführt werden. Dadurch wäre es möglich, einen Überblick über die gebildeten Kristallphasen nach unterschiedlichen Reaktionszeiten direkt auf dem Trog zu erhalten.
Es konnte weiterhin gezeigt werden, dass auch einfache Amphiphile in der Lage sind, die Mineralisation von Calciumphosphat zu steuern. Amphiphile mit Cholesterol als hydrophoben Block bilden offensichtlich besonders stabile Monolagen an der Wasser/Luft-Grenzfläche. Eine Untersuchung des Einflusses ähnlicher Amphiphile mit unterschiedlichen hydrophilen Kopfgruppen auf das Mineralisationsverhalten von Calciumphosphat wäre durchaus interessant.
In the arable soil landscape of hummocky ground moraines, an erosion-affected spatial differentiation of soils can be observed. Man-made erosion leads to soil profile modifications along slopes with changed solum thickness and modified properties of soil horizons due to water erosion in combination with tillage operations. Soil erosion creates, thereby, spatial patterns of soil properties (e.g., texture and organic matter content) and differences in crop development. However, little is known about the manner in which water fluxes are affected by soil-crop interactions depending on contrasting properties of differently-developed soil horizons and how water fluxes influence the carbon transport in an eroded landscape. To identify such feedbacks between erosion-induced soil profile modifications and the 1D-water and solute balance, high-precision weighing lysimeters equipped with a wide range of sensor technique were filled with undisturbed soil monoliths that differed in the degree of past soil erosion. Furthermore, lysimeter effluent concentrations were analyzed for dissolved carbon fractions in bi-weekly intervals.
The water balance components measured by high precision lysimeters varied from the most eroded to the less eroded monolith up to 83 % (deep drainage) primarily caused due to varying amounts of precipitation and evapotranspiration for a 3-years period. Here, interactions between crop development and contrasting rainfall interception by above ground biomass could explain differences in water balance components. Concentrations of dissolved carbon in soil water samples were relatively constant in time, suggesting carbon leaching was mainly affected by water fluxes in this observation period. For the lysimeter-based water balance analysis, a filtering scheme was developed considering temporal autocorrelation. The minute-based autocorrelation analysis of mass changes from lysimeter time series revealed characteristic autocorrelation lengths ranging from 23 to 76 minutes. Thereby, temporal autocorrelation provided an optimal approximation of precipitation quantities. However, the high temporal resolution in lysimeter time series is restricted by the lengths of autocorrelation.
Erosion-induced but also gradual changes in soil properties were reflected by dynamics of soil water retention properties in the lysimeter soils. Short-term and long-term hysteretic water retention data suggested seasonal wettability problems of soils increasingly limited rewetting of previously dried pore regions. Differences in water retention were assigned to soil tillage operations and the erosion history at different slope positions. The threedimensional spatial pattern of soil types that result from erosional soil profile modifications were also reflected in differences of crop root development at different landscape positions. Contrasting root densities revealed positive relations of root and aboveground plant characteristics. Differences in the spatially-distributed root growth between different eroded soil types provided indications that root development was affected by the erosion-induced soil evolution processes.
Overall, the current thesis corroborated the hypothesis that erosion-induced soil profile modifications affect the soil water balance, carbon leaching and soil hydraulic properties, but also the crop root system is influenced by erosion-induced spatial patterns of soil properties in the arable hummocky post glacial soil landscape. The results will help to improve model predictions of water and solute movement in arable soils and to understand interactions between soil erosion and carbon pathways regarding sink-or-source terms in landscapes.
Mathematical models of bacterial growth have been successfully applied to study the relationship between antibiotic drug exposure and the antibacterial effect. Since these models typically lack a representation of cellular processes and cell physiology, the mechanistic integration of drug action is not possible on the cellular level. The cellular mechanisms of drug action, however, are particularly relevant for the prediction, analysis and understanding of interactions between antibiotics. Interactions are also studied experimentally, however, a lacking consent on the experimental protocol hinders direct comparison of results. As a consequence, contradictory classifications as additive, synergistic or antagonistic are reported in literature.
In the present thesis we developed a novel mathematical model for bacterial growth that integrates cell-level processes into the population growth level. The scope of the model is to predict bacterial growth under antimicrobial perturbation by multiple antibiotics in vitro.
To this end, we combined cell-level data from literature with population growth data for Bacillus subtilis, Escherichia coli and Staphylococcus aureus. The cell-level data described growth-determining characteristics of a reference cell, including the ribosomal concentration and efficiency. The population growth data comprised extensive time-kill curves for clinically relevant antibiotics (tetracycline, chloramphenicol, vancomycin, meropenem, linezolid, including dual combinations).
The new cell-level approach allowed for the first time to simultaneously describe single and combined effects of the aforementioned antibiotics for different experimental protocols, in particular different growth phases (lag and exponential phase). Consideration of ribosomal dynamics and persisting sub-populations explained the decreased potency of linezolid on cultures in the lag phase compared to exponential phase cultures. The model captured growth rate dependent killing and auto-inhibition of meropenem and - also for vancomycin exposure - regrowth of the bacterial cultures due to adaptive resistance development. Stochastic interaction surface analysis demonstrated the pronounced antagonism between meropenem and linezolid to be robust against variation in the growth phase and pharmacodynamic endpoint definition, but sensitive to a change in the experimental duration.
Furthermore, the developed approach included a detailed representation of the bacterial cell-cycle. We used this representation to describe septation dynamics during the transition of a bacterial culture from the exponential to stationary growth phase. Resulting from a new mechanistic understanding of transition processes, we explained the lag time between the increase in cell number and bacterial biomass during the transition from the lag to exponential growth phase. Furthermore, our model reproduces the increased intracellular RNA mass fraction during long term exposure of bacteria to chloramphenicol.
In summary, we contribute a new approach to disentangle the impact of drug effects, assay readout and experimental protocol on antibiotic interactions. In the absence of a consensus on the corresponding experimental protocols, this disentanglement is key to translate information between heterogeneous experiments and also ultimately to the clinical setting.
With Saccharomyces cerevisiae being a commonly used host organism for synthetic biology and biotechnology approaches, the work presented here aims at the development of novel tools to improve and facilitate pathway engineering and heterologous protein production in yeast. Initially, the multi-part assembly strategy AssemblX was established, which allows the fast, user-friendly and highly efficient construction of up to 25 units, e.g. genes, into a single DNA construct. To speed up complex assembly projects, starting from sub-gene fragments and resulting in mini-chromosome sized constructs, AssemblX follows a level-based approach: Level 0 stands for the assembly of genes from multiple sub-gene fragments; Level 1 for the combination of up to five Level 0 units into one Level 1 module; Level 2 for linkages of up to five Level 1 modules into one Level 2 module. This way, all Level 0 and subsequently all Level 1 assemblies can be carried out simultaneously. Individually planned, overlap-based Level 0 assemblies enable scar-free and sequence-independent assemblies of transcriptional units, without limitations in fragment number, size or content. Level 1 and Level 2 assemblies, which are carried out via predefined, computationally optimized homology regions, follow a standardized, highly efficient and PCR-free scheme. AssemblX follows a virtually sequence-independent scheme with no need for time-consuming domestication of assembly parts. To minimize the risk of human error and to facilitate the planning of assembly projects, especially for individually designed Level 0 constructs, the whole AssemblX process is accompanied by a user-friendly webtool. This webtool provides the user with an easy-to-use operating surface and returns a bench-protocol including all cloning steps. The efficiency of the assembly process is further boosted through the implementation of different features, e.g. ccdB counter selection and marker switching/reconstitution. Due to the design of homology regions and vector backbones the user can flexibly choose between various overlap-based cloning methods, enabling cost-efficient assemblies which can be carried out either in E. coli or yeast. Protein production in yeast is additionally supported by a characterized library of 40 constitutive promoters, fully integrated into the AssemblX toolbox. This provides the user with a starting point for protein balancing and pathway engineering. Furthermore, the final assembly cassette can be subcloned into any vector, giving the user the flexibility to transfer the individual construct into any host organism different from yeast.
As successful production of heterologous compounds generally requires a precise adjustment of protein levels or even manipulation of the host genome to e.g. inhibit unwanted feedback regulations, the optogenetic transcriptional regulation tool PhiReX was designed. In recent years, light induction was reported to enable easy, reversible, fast, non-toxic and nearly gratuitous regulation, thereby providing manifold advantages compared to conventional chemical inducers. The optogenetic interface established in this study is based on the photoreceptor PhyB and its interacting protein PIF3. Both proteins, derived from Arabidopsis thaliana, dimerize in a red/far-red light-responsive manner. This interaction depends on a chromophore, naturally not available in yeast. By fusing split proteins to both components of the optical dimerizer, active enzymes can be reconstituted in a light-dependent manner. For the construction of the red/far-red light sensing gene expression system PhiReX, a customizable synTALE-DNA binding domain was fused to PhyB, and a VP64 activation domain to PIF3. The synTALE-based transcription factor allows programmable targeting of any desired promoter region. The first, plasmid-based PhiReX version mediates chromophore- and light-dependent expression of the reporter gene, but required further optimization regarding its robustness, basal expression and maximum output. This was achieved by genome-integration of the optical regulator pair, by cloning the reporter cassette on a high-copy plasmid and by additional molecular modifications of the fusion proteins regarding their cellular localization. In combination, this results in a robust and efficient activation of cells over an incubation time of at least 48 h. Finally, to boost the potential of PhiReX for biotechnological applications, yeast was engineered to produce the chromophore. This overcomes the need to supply the expensive and photo-labile compound exogenously. The expression output mediated through PhiReX is comparable to the strong constitutive yeast TDH3 promoter and - in the experiments described here - clearly exceeds the commonly used galactose inducible GAL1 promoter.
The fast-developing field of synthetic biology enables the construction of complete synthetic genomes. The upcoming Synthetic Yeast Sc2.0 Project is currently underway to redesign and synthesize the S. cerevisiae genome. As a prerequisite for the so-called “SCRaMbLE” system, all Sc2.0 chromosomes incorporate symmetrical target sites for Cre recombinase (loxPsym sites), enabling rearrangement of the yeast genome after induction of Cre with the toxic hormonal substance beta-estradiol. To overcome the safety concern linked to the use of beta-estradiol, a red light-inducible Cre recombinase, dubbed L-SCRaMbLE, was established in this study. L-SCRaMbLE was demonstrated to allow a time- and chromophore-dependent recombination with reliable off-states when applied to a plasmid containing four genes of the beta-carotene pathway, each flanked with loxPsym sites. When directly compared to the original induction system, L-SCRaMbLE generates a larger variety of recombination events and lower basal activity. In conclusion, L-SCRaMbLE provides a promising and powerful tool for genome rearrangement.
The three tools developed in this study provide so far unmatched possibilities to tackle complex synthetic biology projects in yeast by addressing three different stages: fast and reliable biosynthetic pathway assembly; highly specific, orthogonal gene regulation; and tightly controlled synthetic evolution of loxPsym-containing DNA constructs.
Im Fokus der kumulativen Dissertationsschrift stehen Grundschullehrerinnen und Grundschullehrer in ihrer Rolle als Diagnostikerinnen und Diagnostiker. Exemplarisch werden mit der Einschätzung von Aufgabenschwierigkeiten und der Feststellung von Sprachförderbedarf zwei diagnostische Herausforderungen untersucht, die Lehrkräfte an Grundschulen bewältigen müssen.
Die vorliegende Arbeit umfasst drei empirische Teilstudien, die in einem Rahmentext integriert sind, in dem zunächst die theoretischen Hintergründe und die empirische Befundlage erläutert werden. Hierbei wird auf die diagnostische Kompetenz von Lehrkräften bzw. die Genauigkeit von Lehrerurteilen eingegangen. Ferner wird der Einsatz standardisierter Testinstrumente als wichtiger Bestandteil des diagnostischen Aufgabenfeldes von Lehrkräften charakterisiert. Außerdem werden zentrale Aspekte der Sprachdiagnostik in der Grundschule dargestellt.
In Teilstudie 1 (Hoffmann & Böhme, 2014b) wird der Frage nachgegangen, wie akkurat Grundschullehrerinnen und -lehrer die Schwierigkeit von Deutsch- und Mathematikaufgaben einschätzen. Darüber hinaus wird untersucht, welche Faktoren mit der Über- oder Unterschätzung der Schwierigkeit von Aufgaben zusammenhängen.
In Teilstudie 2 (Hoffmann & Böhme, 2017) wird geprüft, inwiefern die Klassifikationsgüte von Entschei¬dungen zum sprachlichen Förderbedarf mit den hierfür genutzten diagnostischen Informationsquellen kovariiert. Der Fokus liegt hierbei vor allem auf der Untersuchung von Effekten des Einsatzes von sprachdiagnostischen Verfahren.
Teilstudie 3 (Hoffmann, Böhme & Stanat, 2017) untersucht schließlich die Frage, welche diagnostischen Verfahren gegenwärtig bundesweit an den Grundschulen zur Feststellung sprachlichen Förderbedarfs genutzt werden und ob diese Verfahren etwa testtheoretischen Gütekriterien genügen.
Die zentralen Ergebnisse der Teilstudien werden im Rahmentext zusammen¬gefasst und studienübergreifend diskutiert. Hierbei wird auch auf methodische Stärken und Schwächen der drei Beiträge sowie auf Implikationen für die zukünftige Forschung und die schulische Praxis hingewiesen.
Prosody is a rich source of information that heavily supports spoken language comprehension. In particular, prosodic phrase boundaries divide the continuous speech stream into chunks reflecting the semantic and syntactic structure of an utterance. This chunking or prosodic phrasing plays a critical role in both spoken language processing and language acquisition. Aiming at a better understanding of the underlying processing mechanisms and their acquisition, the present work investigates factors that influence prosodic phrase boundary perception in adults and infants. Using the event-related potential (ERP) technique, three experimental studies examined the role of prosodic context (i.e., phrase length) in German phrase boundary perception and of the main prosodic boundary cues, namely pitch change, final lengthening, and pause. With regard to the boundary cues, the dissertation focused on the questions which cues or cue combination are essential for the perception of a prosodic boundary and on whether and how this cue weighting develops during infancy.
Using ERPs is advantageous because the technique captures the immediate impact of (linguistic) information during on-line processing. Moreover, as it can be applied independently of specific task demands or an overt response performance, it can be used with both infants and adults. ERPs are particularly suitable to study the time course and underlying mechanisms of boundary perception, because a specific ERP component, the Closure Positive Shift (CPS) is well established as neuro-physiological indicator of prosodic boundary perception in adults.
The results of the three experimental studies first underpin that the prosodic context plays an immediate role in the processing of prosodic boundary information. Moreover, the second study reveals that adult listeners perceive a prosodic boundary also on the basis of a sub-set of the boundary cues available in the speech signal. Both ERP and simultaneously collected behavioral data (i.e., prosodic judgements) suggest that the combination of pitch change and final lengthening triggers boundary perception; however, when presented as single cues, neither pitch change nor final lengthening were sufficient. Finally, testing six- and eight-month-old infants shows that the early sensitivity for prosodic information is reflected in a brain response resembling the adult CPS. For both age groups, brain responses to prosodic boundaries cued by pitch change and final lengthening revealed a positivity that can be interpreted as a CPS-like infant ERP component. In contrast, but comparable to the adults’ response pattern, pitch change as a single cue does not provoke an infant CPS. These results show that infant phrase boundary perception is not exclusively based on pause detection and hint at an early ability to exploit subtle, relational prosodic cues in speech perception.
Dark matter, DM, has not yet been directly observed, but it has a very solid theoretical basis. There are observations that provide indirect evidence, like galactic rotation curves that show that the galaxies are rotating too fast to keep their constituent parts, and galaxy clusters that bends the light coming from behind-lying galaxies more than expected with respect to the mass that can be calculated from what can be visibly seen. These observations, among many others, can be explained with theories that include DM. The missing piece is to detect something that can exclusively be explained by DM. Direct observation in a particle accelerator is one way and indirect detection using telescopes is another. This thesis is focused on the latter method.
The Very Energetic Radiation Imaging Telescope Array System, V ERITAS, is a telescope array that detects Cherenkov radiation. Theory predicts that DM particles annihilate into, e.g., a γγ pair and create a distinctive energy spectrum when detected by such telescopes, e.i., a monoenergetic line at the same energy as the particle mass. This so called ”smoking-gun” signature is sought with a sliding window line search within the sub-range ∼ 0.3 − 10 TeV of the VERITAS energy range, ∼ 0.01 − 30 TeV.
Standard analysis within the VERITAS collaboration uses Hillas analysis and look-up tables, acquired by analysing particle simulations, to calculate the energy of the particle causing the Cherenkov shower. In this thesis, an improved analysis method has been used. Modelling each shower as a 3Dgaussian should increase the energy recreation quality. Five dwarf spheroidal galaxies were chosen as targets with a total of ∼ 224 hours of data. The targets were analysed individually and stacked. Particle simulations were based on two simulation packages, CARE and GrISU.
Improvements have been made to the energy resolution and bias correction, up to a few percent each, in comparison to standard analysis. Nevertheless, no line with a relevant significance has been detected. The most promising line is at an energy of ∼ 422 GeV with an upper limit cross section of 8.10 · 10^−24 cm^3 s^−1 and a significance of ∼ 2.73 σ, before trials correction and ∼ 1.56 σ after. Upper limit cross sections have also been calculated for the γγ annihilation process and four other outcomes. The limits are in line with current limits using other methods, from ∼ 8.56 · 10^−26 − 6.61 · 10^−23 cm^3s^−1. Future larger telescope arrays, like the upcoming Cherenkov Telescope Array, CTA, will provide better results with the help of this analysis method.
In der vorliegenden Dissertation werden lebensweltliche Erfahrungszusammenhänge in 128 Aufsätzen ausländischer Studierender, die oft auch als Bildungsausländer bezeichnet werden, und grundsätzliche Prozesse bei der Herausbildung sowie Veränderung kollektiver Zuschreibungen im Rahmen der sozialen Identitätsbildung hermeneutisch untersucht.
Mit Hilfe der nach der empirischen Methode der Grounded Theory kodierten Interpretationsergebnisse werden in der qualitativen Längsschnittstudie Vergleiche angestellt, sowohl fallintern als auch fallübergreifend, um Muster zu entdecken, Typologien zu konstruieren und die jeweiligen (kulturellen) Horizonte in den Aufsätzen zu verallgemeinern.
Neben der Grounded Theory bildet die Theorie der „alltäglichen Lebenswelt“ (Alfred Schütz) eine Basis der Herangehensweise an die Untersuchung der Aufsätze. In diesem Kontext wird ausgehend von der graduellen Unterteilung der Fremdheit in alltägliche, strukturelle und radikale Fremdheit sowie ausgehend von Goffmans Identitätskonzept der Frage nachgegangen, inwieweit sich in den untersuchten Texten die Bildung und Veränderung sozialer Identitäten feststellen lassen. Dabei werden Akkulturationsprozesse und Prozesse der Selbstidentifikation, bezüglich einer angenommenen Gemeinschaft, analysiert, die von kollektiven (kulturellen) Schemata bestimmt sind. In diesem Zusammenhang kann die vorliegende Dissertation zeigen, dass sich bestimmte kulturelle Schemata in der Auseinandersetzung mit dem vormals neuen Leben in Deutschland herausgebildet haben und bestimmte ältere Erfahrungen immer wieder zur Bestätigung dieser Bilder bzw. Erfahrungsschemata herangezogen und wie der Abdruck in Gestein fossiliert werden.
Herstellung anisotroper Kolloide mittels templatgesteuerter Assemblierung und Kontaktdruckverfahren
(2017)
Diese Arbeit befasste sich mit neuen Konzepten zur Darstellung anisotroper Partikelsysteme durch Anordnung von funktionalisierten Partikeln unter Zuhilfenahme etablierter Methoden wie der templatgestützten Assemblierung von Partikeln und dem Mikrokontaktdruck.
Das erste Teilprojekt beschäftigte sich mit der kontrollierten Herstellung von Faltenstrukturen im Mikro- bis Nanometerbereich. Die Faltenstrukturen entstehen durch die Relaxation eines Systems bestehend aus zwei übereinander liegender Schichten unterschiedlicher Elastizität. In diesem Fall wurden Falten auf einem elastischen PDMS-Substrat durch Generierung einer Oxidschicht auf der Substratoberfläche mittels Plasmabehandlung erzeugt. Die Dicke der Oxidschicht, die über verschiedene Parameter wie Behandlungszeit, Prozessleistung, Partialdruck des plasmaaktiven Gases, Vernetzungsgrad, Deformation sowie Substratdicke einstellbar war, bestimmte Wellenlänge und Amplitude der Falten.
Das zweite Teilprojekt hatte die Darstellung komplexer, kolloidaler Strukturen auf Basis supramolekularer Wechselwirkungen zum Ziel. Dazu sollte vor allem die templatgestützte Assemblierung von Partikeln sowohl an fest-flüssig als auch flüssig-flüssig Grenzflächen genutzt werden. Für Erstere sollten die in Teilprojekt 1 hergestellten Faltenstrukturen als Templat, für Letztere Pickering-Emulsionen zur Anwendung kommen. Im ersten Fall wurden verschiedene, modifizierte Silicapartikel und Magnetitnanopartikel, deren Größe und Oberflächenfunktionalität (Cyclodextrin-, Azobenzol- und Arylazopyrazolgruppen) variierte, in Faltenstrukturen angeordnet. Die Anordnung hing dabei nicht nur vom gewählten Verfahren, sondern auch von Faktoren wie der Partikelkonzentration, der Oberflächenladung oder dem Größenverhältnis der Partikel zur Faltengeometrie ab.
Die Kombination von Cyclodextrin (CD)- und Arylazopyrazol-modifizierten Partikeln ermöglichte, auf Basis einer Wirt-Gast-Wechselwirkung zwischen den Partikeltypen und einer templatgesteuerten Anordnung, die Bildung komplexer und strukturierter Formen in der Größenordnung mehrerer Mikrometer. Dieses System kann einerseits als Grundlage für die Herstellung verschiedener Janus-Partikel herangezogen werden, andererseits stellt die gerichtete Vernetzung zweier Partikelsysteme zu größeren Aggregaten den Grundstein für neuartige, funktionale Materialien dar. Neben der Anordnung an fest-flüssig Grenzflächen konnte außerdem nachgewiesen werden, dass Azobenzol-funktionalisierte Silicapartikel in der Lage sind, Pickering-Emulsionen über mehrere Monate zu stabilisieren. Die Stabilität und Größe der Emulsionsphase kann über Parameter, wie das Volumenverhältnis und die Konzentration, gesteuert werden. CD-funktionalisierte Silicapartikel besaßen dagegen keine Grenzflächenaktivität, während es CD-basierten Polymeren wiederum möglich war, durch die Ausbildung von Einschlusskomplexen mit den hydrophoben Molekülen der Ölphase stabile Emulsionen zu bilden. Dagegen zeigte die Kombination zwei verschiedener Partikelsysteme keinen oder einen destabilisierenden Effekt bezüglich der Ausbildung von Emulsionen.
Im letzten Teilprojekt wurde die Herstellung multivalenter Silicapartikel mittels Mikrokontaktdruck untersucht. Die Faltenstrukturen wurden dabei als Stempel verwendet, wodurch es möglich war, die Patch-Geometrie über die Wellenlänge der Faltenstrukturen zu steuern. Als Tinte diente das positiv geladene Polyelektrolyt Polyethylenimin (PEI), welches über elektrostatische Wechselwirkungen auf unmodifizierten Silicapartikeln haftet. Im Gegensatz zum Drucken mit flachen Stempeln fiel dabei zunächst auf, dass sich die Tinte bei den Faltenstrukturen nicht gleichmäßig über die gesamte Substratfläche verteilt, sondern hauptsächlich in den Faltentälern vorlag. Dadurch handelte es sich bei dem Druckprozess letztlich nicht mehr um ein klassisches Mikrokontaktdruckverfahren, sondern um ein Tiefdruckverfahren. Über das Tiefdruckverfahren war es dann aber möglich, sowohl eine als auch beide Partikelhemisphären gleichzeitig und mit verschiedenen Funktionalitäten zu modifizieren und somit multivalente Silicapartikel zu generieren. In Abhängigkeit der Wellenlänge der Falten konnten auf einer Partikelhemisphäre zwei bis acht Patches abgebildet werden. Für die Patch-Geometrie, sprich Größe und Form der Patches, spielten zudem die Konzentration der Tinte auf dem Stempel, das Lösungsmittel zum Ablösen der Partikel nach dem Drucken sowie die Stempelhärte eine wichtige Rolle. Da die Stempelhärte aufgrund der variierenden Dicke der Oxidschicht bei verschiedenen Wellenlängen nicht kontant ist, wurden für den Druckprozess meist Abgüsse der Faltensubstrate verwendet. Auf diese Weise war auch die Vergleichbarkeit bei variierender Wellenlänge gewährleistet. Neben dem erfolgreichen Nachweis der Modifikation mittels Tiefdruckverfahren konnte auch gezeigt werden, dass über die Komplexierung mit PEI negativ geladene Nanopartikel auf die Partikeloberfläche aufgebracht werden können.
Among modern functional materials, the class of nitrogen-containing carbons combines non-toxicity and sustainability with outstanding properties. The versatility of this materials class is based on the opportunity to tune electronic and catalytic properties via the nitrogen content and –motifs: This ranges from the electronically conducting N-doped carbon, where few carbon atoms in the graphitic lattice are substituted by nitrogen, to the organic semiconductor graphitic carbon nitride (g-C₃N₄), with a structure based on tri-s-triazine units.
In general, composites can reveal outstanding catalytic properties due to synergistic behavior, e.g. the formation of electronic heterojunctions. In this thesis, the formation of an “all-carbon” heterojunction was targeted, i.e. differences in the electronic properties of the single components were achieved by the introduction of different nitrogen motives into the carbon lattice. Such composites are promising as metal-free catalysts for the photocatalytic water splitting. Here, hydrogen can be generated from water by light irradiation with the use of a photocatalyst. As first part of the heterojunction, the organic semiconductor g-C₃N₄ was employed, because of its suitable band structure for photocatalytic water splitting, high stability and non-toxicity. The second part was chosen as C₂N, a recently discovered semiconductor. Compared to g-C₃N₄, the less nitrogen containing C₂N has a smaller band gap and a higher absorption coefficient in the visible light range, which is expected to increase the optical absorption in the composite eventually leading to an enhanced charge carrier separation due to the formation of an electronic heterojunction.
The aim of preparing an “all-carbon” composite included the research on appropriate precursors for the respective components g-C₃N₄ and C₂N, as well as strategies for appropriate structuring. This was targeted by applying precursors which can form supramolecular pre-organized structures. This allows for more control over morphology and atom patterns during the carbonization process.
In the first part of this thesis, it was demonstrated how the photocatalytic activity of g-C₃N₄ can be increased by the targeted introduction of defects or surface terminations. This was achieved by using caffeine as a “growth stopping” additive during the formation of the hydrogen-bonded supramolecular precursor complexes. The increased photocatalytic activity of the obtained materials was demonstrated with dye degradation experiments.
The second part of this thesis was focused on the synthesis of the second component C₂N. Here, a deep eutectic mixture from hexaketocyclohexane and urea was structured using the biopolymer chitosan. This scaffolding resulted in mesoporous nitrogen-doped carbon monoliths and beads. CO₂- and dye-adsorption experiments with the obtained monolith material revealed a high isosteric heat of CO₂-adsorption and showed the accessibility of the monolithic pore system to larger dye molecules. Furthermore, a novel precursor system for C₂N was explored, based on organic crystals from squaric acid and urea. The respective C₂N carbon with an unusual sheet-like morphology could be synthesized by carbonization of the crystals at 550 °C. With this precursor system, also microporous C₂N carbon with a BET surface area of 865 m²/g was obtained by “salt-templating” with ZnCl₂.
Finally, the preparation of a g-C₃N₄/C₂N “all carbon” composite heterojunction was attempted by the self-assembly of g-C₃N₄ and C₂N nanosheets and tested for photocatalytic water splitting. Indeed, the composites revealed high rates of hydrogen evolution when compared to bulk g-C₃N₄. However, the increased catalytic activity was mainly attributed to the high surface area of the nanocomposites rather than to the composition. With regard to alternative composite synthesis ways, first experiments indicated N-Methyl-2-pyrrolidon to be suitable for higher concentrated dispersion of C₂N nanosheets. Eventually, the results obtained in this thesis provide precious synthetic contributions towards the preparation and processing of carbon/nitrogen compounds for energy applications.
Die vorliegende Arbeit mit dem Titel „Eine Frage der Zeit. Wie Einflüsse individueller Merkmale auf Einkommen bei Frauen über ihre familiären Verpflichtungen vermittelt werden“ geht der Frage der Heterogenität bei weiblichen Einkommensergebnissen nach. Dabei steht die Thematik der individuellen Investitionen in die familiäre Arbeit als erklärender Faktor im Vordergrund und es wird der Frage nachgegangen, warum die einen Frauen viele und andere weniger häusliche Verpflichtungen übernehmen. Hierfür werden das individuelle Humankapital der Frauen, ihre Werteorientierungen und individuelle berufliche Motivationen aus der Jugendzeit und im Erwachsenenalter herangezogen. Die analysierten Daten (Daten der LifE-Studie) repräsentieren eine Langzeitperspektive vom 16. bis zum 45. Lebensjahr der befragten Frauen. Zusammenfassend kann im Ergebnis gezeigt werden, dass ein Effekt familiärer Verpflichtungen auf Einkommensergebnisse bei Frauen im frühen und mittleren Erwachsenenalter als Zeiteffekt über die investierte Erwerbsarbeitszeit vermittelt wird. Die Relevanz privater Routinearbeiten für Berufserfolge von Frauen und insbesondere Müttern stellt somit eine Frage der Zeit dar. Weiterhin kann für individuelle Einflüsse auf Einkommen bei Frauen gezeigt werden, dass höhere zeitliche Investitionen in den Beruf von Frauen mit hohem Bildungsniveau als indirect-only-Mediation nur über die Umverteilung häuslicher Arbeiten erklärbar werden. Frauen sind demnach zwar Gewinnerinnen der Bildungsexpansion. Die Bildungsexpansion stellt jedoch auch die Geschichte der Entstehung eines Vereinbarkeitskonflikts für eben diese Frauen dar, weil die bis heute virulenten Beharrungskräfte hinsichtlich der Frauen zugeschriebenen familiären Verpflichtungen mit ihren gestiegenen beruflichen Erwartungen und Chancen kollidieren. Die Arbeit leistet in ihren Analyseresultaten einen wichtigen Beitrag zur Erklärung heterogener Investitionen von Frauen in den Beruf und ihrer Einkommensergebnisse aus dem Privaten heraus.
Background: Obesity is thought to be the consequence of an unhealthy nutrition and a lack of physical activity. Although the resulting metabolic alterations such as impaired glucose homeostasis and insulin sensitivity can usually be improved by physical activity, some obese patients fail to enhance skeletal muscle metabolic health with exercise training. Since this might be largely heritable, maternal nutrition during pregnancy and lactation is hypothesized to impair offspring skeletal muscle physiology.
Objectives: This PhD thesis aims to investigate the consequences of maternal high-fat diet (mHFD) consumption on offspring skeletal muscle physiology and exercise performance. We could show that maternal high-fat diet during gestation and lactation decreases the offspring’s training efficiency and endurance performance by influencing the epigenetic profile of their skeletal muscle and altering the adaptation to an acute exercise bout, which in long-term, increases offspring obesity susceptibility.
Experimental setup: To investigate this issue in detail, we conducted several studies with a similar maternal feeding regime. Dams (C57BL/6J) were either fed a low-fat diet (LFD; 10 energy% from fat) or high-fat diet (HFD; 40 energy% from fat) during pregnancy and lactation. After weaning, male offspring of both maternal groups were switched to a LFD, on which they remained until sacrifice in week 6, 15 or 25. In one study, LFD feeding was followed by HFD provision from week 15 until week 25 to elucidate the effects on offspring obesity susceptibility. In week 7, all mice were randomly allocated to a sedentary group (without running wheel) or an exercised group (with running wheel for voluntary exercise training). Additionally, treadmill endurance tests were conducted to investigate training performance and efficiency. In order to uncover regulatory mechanisms, each study was combined with a specific analytical setup, such as whole genome microarray analysis, gene and protein expression analysis, DNA methylation analyses, and enzyme activity assays.
Results: mHFD offspring displayed a reduced training efficiency and endurance capacity. This was not due to an altered skeletal muscle phenotype with changes in fiber size, number, and type. DNA methylation measurements in 6 week old offspring showed a hypomethylation of the Nr4a1 gene in mHFD offspring leading to an increased gene expression. Since Nr4a1 plays an important role in the regulation of skeletal muscle energy metabolism and early exercise adaptation, this could affect offspring training efficiency and exercise performance in later life.
Investigation of the acute response to exercise showed that mHFD offspring displayed a reduced gene expression of vascularization markers (Hif1a, Vegfb, etc) pointing towards a reduced angiogenesis which could possibly contribute to their reduced endurance capacity. Furthermore, an impaired glucose utilization of skeletal muscle during the acute exercise bout by an impaired skeletal muscle glucose handling was evidenced by higher blood glucose levels, lower GLUT4 translocation and diminished Lactate dehydrogenase activity in mHFD offspring immediately after the endurance test. These points towards a disturbed use of glucose as a substrate during endurance exercise. Prolonged HFD feeding during adulthood increases offspring fat mass gain in mHFD offspring compared to offspring from low-fat fed mothers and also reduces their insulin sensitivity pointing towards a higher obesity and diabetes susceptibility despite exercise training. Consequently, mHFD reduces offspring responsiveness to the beneficial effects of voluntary exercise training.
Conclusion: The results of this PhD thesis demonstrate that mHFD consumption impairs the offspring’s training efficiency and endurance capacity, and reduced the beneficial effects of exercise on the development of diet-induced obesity and insulin resistance in the offspring.
This might be due to changes in skeletal muscle epigenetic profile and/or an impaired skeletal muscle angiogenesis and glucose utilization during an acute exercise bout, which could contribute to a disturbed adaptive response to exercise training.
Die Arktis erwärmt sich schneller als der Rest der Erde. Die Auswirkungen manifestieren sich unter Anderem in einer verstärkten Erwärmung der arktischen Grenzschicht. Diese Arbeit befasst sich mit Wechselwirkungen zwischen synoptischen Zyklonen und der arktischen Atmosphäre auf lokalen bis überregionalen Skalen. Ausgangspunkt dafür sind Messdaten und Modellsimulationen für den Zeitraum der N-ICE2015 Expedition, die von Anfang Januar bis Ende Juni 2015 im arktischen Nordatlantiksektor stattgefunden hat.
Anhand von Radiosondenmessungen lassen sich Auswirkungen von synoptischen Zyklonen am deutlichsten im Winter erkennen, da sie durch die Advektion warmer und feuchter Luftmassen in die Arktis den Zustand der Atmosphäre von einem strahlungs-klaren in einen strahlungs-opaken ändern. Obwohl dieser scharfe Kontrast nur im Winter existiert, zeigt die Analyse, dass der integrierte Wasserdampf als Indikator für die Advektion von Luftmassen aus niedrigen Breiten in die Arktis auch im Frühjahr geeignet ist. Neben der Advektion von Luftmassen wird der Einfluss der Zyklonen auf die statische Stabilität charakterisiert. Beim Vergleich der N-ICE2015 Beobachtungen mit der SHEBA Kampagne (1997/1998), die über dickerem Eis stattfand, finden sich trotz der unterschiedlichen Meereisregime Ähnlichkeiten in der statischen Stabilität der Atmosphäre. Die beobachteten Differenzen in der Stabilität lassen sich auf Unterschiede in der synoptischen Aktivität zurückführen. Dies lässt vermuten, dass die dünnere Eisdecke auf saisonalen Zeitskalen nur einen geringen Einfluss auf die thermodynamische Struktur der arktischen Troposphäre besitzt, solange eine dicke Schneeschicht sie bedeckt. Ein weiterer Vergleich mit den parallel zur N-ICE2015 Kampagne gestarteten Radiosonden der AWIPEV Station in Ny-Åesund, Spitzbergen, macht deutlich, dass die synoptischen Zyklonen oberhalb der Orographie auf saisonalen Zeitskalen das Wettergeschehen bestimmen.
Des Weiteren werden für Februar 2015 die Auswirkungen von in der Vertikalen variiertem Nudging auf die Entwicklung der Zyklonen am Beispiel des hydrostatischen regionalen Klimamodells HIRHAM5 untersucht. Es zeigt sich, dass die Unterschiede zwischen den acht Modellsimulationen mit abnehmender Anzahl der genudgten Level zunehmen. Die größten Differenzen resultieren vornehmlich aus dem zeitlichen Versatz der Entwicklung synoptischer Zyklonen. Zur Korrektur des Zeitversatzes der Zykloneninitiierung genügt es bereits, Nudging in den unterstem 250 m der Troposphäre anzuwenden. Daneben findet sich zwischen den genudgten HIRHAM5-Simulation und den in situ Messungen der gleiche positive Temperaturbias, den auch ERA-Interim besitzt. Das freie HIRHAM hingegen reproduziert das positive Ende der N-ICE2015 Temperaturverteilung gut, besitzt aber einen starken negativen Bias, der sehr wahrscheinlich aus einer Unterschätzung des Feuchtegehalts resultiert. An Beispiel einer Zyklone wird gezeigt, dass Nudging Einfluss auf die Lage der Höhentiefs besitzt, die ihrerseits die Zyklonenentwicklung am Boden beeinflussen. Im Weiteren wird mittels eines für kleine Ensemblegrößen geeigneten Varianzmaßes eine statistische Einschätzung der Wirkung des Nudgings auf die Vertikale getroffen. Es wird festgestellt, dass die Ähnlichkeit der Modellsimulationen in der unteren Troposphäre generell höher ist als darüber und in 500 hPa ein lokales Minimum besitzt.
Im letzten Teil der Analyse wird die Wechselwirkung der oberen und unteren Stratosphäre anhand zuvor betrachteter Zyklonen mit Daten der ERA-Interim Reanalyse untersucht. Lage und Ausrichtung des Polarwirbels erzeugten ab Anfang Februar 2015 eine ungewöhnlich große Meridionalkomponente des Tropopausenjets, die Zugbahnen in die zentrale Arktis begünstigte. Am Beispiel einer Zyklone wird die Übereinstimmung der synoptischen Entwicklung mit den theoretischen Annahmen über den abwärts gerichteten Einfluss der Stratosphäre auf die Troposphäre hervorgehoben. Dabei spielt die nicht-lineare Wechselwirkung zwischen der Orographie Grönlands, einer Intrusion stratosphärischer Luft in die Troposphäre sowie einer in Richtung Arktis propagierender Rossby-Welle eine tragende Rolle. Als Indikator dieser Wechselwirkung werden horizontale Signaturen aus abwechselnd aufsteigender und absinkender Luft innerhalb der Troposphäre identifiziert.
Natural hazards can have serious societal and economic impacts. Worldwide, around one third of economic losses due to natural hazards are attributable to floods. The majority of natural hazards are triggered by weather-related extremes such as heavy precipitation, rapid snow melt, or extreme temperatures. Some of them, and in particular floods, are expected to further increase in terms of frequency and/or intensity in the coming decades due to the impacts of climate change. In this context, the European Alps areas are constantly disclosed as being particularly sensitive.
In order to enhance the resilience of societies to natural hazards, risk assessments are substantial as they can deliver comprehensive risk information to be used as a basis for effective and sustainable decision-making in natural hazards management. So far, current assessment approaches mostly focus on single societal or economic sectors – e.g. flood damage models largely concentrate on private-sector housing – and other important sectors, such as the transport infrastructure sector, are widely neglected. However, transport infrastructure considerably contributes to economic and societal welfare, e.g. by ensuring mobility of people and goods. In Austria, for example, the national railway network is essential for the European transit of passengers and freights as well as for the development of the complex Alpine topography. Moreover, a number of recent experiences show that railway infrastructure and transportation is highly vulnerable to natural hazards. As a consequence, the Austrian Federal Railways had to cope with economic losses on the scale of several million euros as a result of flooding and other alpine hazards.
The motivation of this thesis is to contribute to filling the gap of knowledge about damage to railway infrastructure caused by natural hazards by providing new risk information for actors and stakeholders involved in the risk management of railway transportation. Hence, in order to support the decision-making towards a more effective and sustainable risk management, the following two shortcomings in natural risks research are approached: i) the lack of dedicated models to estimate flood damage to railway infrastructure, and ii) the scarcity of insights into possible climate change impacts on the frequency of extreme weather events with focus on future implications for railway transportation in Austria.
With regard to flood impacts to railway infrastructure, the empirically derived damage model Railway Infrastructure Loss (RAIL) proved expedient to reliably estimate both structural flood damage at exposed track sections of the Northern Railway and resulting repair cost. The results show that the RAIL model is capable of identifying flood risk hot spots along the railway network and, thus, facilitates the targeted planning and implementation of (technical) risk reduction measures. However, the findings of this study also show that the development and validation of flood damage models for railway infrastructure is generally constrained by the continuing lack of detailed event and damage data.
In order to provide flood risk information on the large scale to support strategic flood risk management, the RAIL model was applied for the Austrian Mur River catchment using three different hydraulic scenarios as input as well as considering an increased risk aversion of the railway operator. Results indicate that the model is able to deliver comprehensive risk information also on the catchment level. It is furthermore demonstrated that the aspect of risk aversion can have marked influence on flood damage estimates for the study area and, hence, should be considered with regard to the development of risk management strategies.
Looking at the results of the investigation on future frequencies of extreme weather events jeopardizing railway infrastructure and transportation in Austria, it appears that an increase in intense rainfall events and heat waves has to be expected, whereas heavy snowfall and cold days are likely to decrease. Furthermore, results indicate that frequencies of extremes are rather sensitive to changes of the underlying thresholds. It thus emphasizes the importance to carefully define, validate, and — if needed — to adapt the thresholds that are used to detect and forecast meteorological extremes. For this, continuous and standardized documentation of damaging events and near-misses is a prerequisite.
Overall, the findings of the research presented in this thesis agree on the necessity to improve event and damage documentation procedures in order to enable the acquisition of comprehensive and reliable risk information via risk assessments and, thus, support strategic natural hazards management of railway infrastructure and transportation.
Magnetotactic bacteria possess an intracellular structure called the magnetosome chain. Magnetosome chains contain nano−particles of iron crystals enclosed by a membrane and aligned on a cytoskeletal filament. Due to the presence of the magnetosome chains, magnetotactic bacteria are able to orient and swim along the magnetic field lines. A detailed study of structural properties of magnetosome chains in magnetotactic bacteria has primary scientific interests. It can provide more insight into the formation of the cytoskeleton in bacteria. In this thesis, we develop a new framework to study the structural properties of magnetosome chains in magnetotactic bacteria.
First, we address the bending stiffness of magnetosome chains resulting from two main contributions: the magnetic interactions of magnetosome particles and the bending stiffness of the cytoskeletal filament to which the magnetosomes are anchored. Our analysis indicates that the linear configuration of magnetosome particles without the stabilisation to the cytoskeleton may close to ring like structures, with no net magnetic moment, which thus can not perform as a compass in cellular navigation. As a result we think that one of the roles of the filament is to stabilize the linear configuration against ring closure.
We then investigate the equilibrium configurations of magnetosome particles including linear chain and closed−ring structures. We notably observe that for the formation of a stable linear structure on the cytoskeletal filament, presence of a binding energy is needed. In the presence of external stimuli the stability of the magnetosome chain is due to the internal dipole−dipole interactions, the stiffness and the binding energy of the protein structure connecting the magnetosome particles to the filament. Our observations, during and after the treatment of the magnetosome chain with the external magnetic field substantiates the stabilisation of magnetosome chains to the cytoskeletal filament by proteinous linkers and the dynamic feature of these structures.
Finally, we employ our model to study the FMR spectra of magnetosome chains in a single cell of magnetotactic bacteria. We explore the effect of magnetocrystalline anisotropy in three-fold symmetry observed in FMR spectra and the peculiarity of different spectra arisen from different mutants of these bacteria.
BACKGROUND: Aggressive behavior at an early age is linked to a broad range of psychosocial problems in later life. That is why risk factors of the occurrence and the development of aggression have been examined for a long time in psychological science. The present doctoral dissertation aims to expand this research by investigating risk factors in three intrapersonal domains using the prominent social-information processing approach by Crick and Dodge (1994) as a framework model. Anger regulation was examined as an affective, theory of mind as a cognitive, and physical attractiveness as an appearance-related developmental factor of aggression in middle childhood. An additional goal of this work was to develop and validate a behavioral observation assessment of anger regulation as past research lacked in ecologically valid measures of anger regulation that are applicable for longitudinal studies.
METHODS: Three empirical studies address the aforementioned intrapersonal risk factors. In each study, data from the PIER-project were used, a three-wave-longitudinal study covering three years with a total sample size of 1,657 children in the age between 6 and 11 years (at the first measurement point). The central constructs were assessed via teacher-reports (aggression), behavioral observation (anger regulation), computer tests (theory of mind), and independent ratings (physical attractiveness). The predictive value of each proposed risk factor for the development of aggressive behavior was examined via structural equation modeling.
RESULTS AND CONCLUSION: The newly developed behavioral observation measure was found to be a reliable and valid tool to assess anger regulation in middle childhood, but limited in capturing a full range of relevant regulation strategies. That might be the reason, why maladaptive anger regulation was not found to function as a risk factor of subsequent aggressive behavior. However, children’s deficits in theory of mind and a low level in physical attractiveness significantly predicted later aggression. Problematic peer relationships were identified as underlying the link between low attractiveness and aggression. Thus, fostering children’s skills in theory of mind and their ability to call existing beliefs about the nature of more versus less attractive individuals into question may be important starting points for the prevention of aggressive behavior in middle childhood.
Natural and potentially hazardous events occur on the Earth’s surface every day. The most destructive of these processes must be monitored, because they may cause loss of lives, infrastructure, and natural resources, or have a negative effect on the environment. A variety of remote sensing technologies allow the recoding of data to detect these processes in the first place, partly based on the diagnostic landforms that they form. To perform this effectively, automatic methods are desirable.
Universal detection of natural hazards is challenging due to their differences in spatial impacts, timing and longevity of consequences, and the spatial resolution of remote-sensing data. Previous studies have reported that topographic metrics such as roughness, which can be captured from digital elevation data, can reveal landforms diagnostic of natural hazards, such as gullies, dunes, lava fields, landslides and snow avalanches, as these landforms tend to be more heterogeneous than the surrounding landscape. A single roughness metric is often limited in such detections; however, a more complex approach that exploits the spatial relation and the location of objects, such as object-based image analysis (OBIA), is desirable.
In this thesis, I propose a topographic roughness measure derived from an airborne laser scanning (ALS) digital terrain model (DTM) and discuss its performance in detecting landforms principally diagnostic of natural hazards. I further develop OBIA-based algorithms for the detection of snow avalanches using near-infrared (NIR) aerial images, and the size (changes) of mountain lakes using LANDSAT satellite images. I quantitatively test and document how the level of difficulty in detecting these very challenging landforms depends on the input data resolution, the derivatives that could be evaluated from images and DTMs, the size, shape and complexity of landforms, and the capabilities of obtaining the information in the data. I demonstrate that surface roughness is a promising metric for detecting different landforms in diverse environments, and that OBIA assists significantly in detecting parts of lakes and snow avalanches that may not be correctly assigned by applying only the thresholding of spectral properties of data and their derivatives.
The curvature-based surface roughness parameter allows the detection of gullies, dunes, lava fields and landslides with a user’s accuracy of 0.63, 0.21, 0.53, and 0.45, respectively. The OBIA algorithms for detecting lakes and snow avalanches obtained user’s accuracy of 0.98, and 0.78, respectively. Most of the analysed landforms constituted only a small part of the entire dataset, and therefore the user’s accuracy is the most appropriate performance measure that should be given in a such classification, because it tells how many automatically-extracted pixels in fact represent the object that one wants to classify, and its calculation does not take the second (background) class into account. One advantage of the proposed roughness parameter is that it allows the extraction of the heterogeneity of the surface without the need for data detrending. The OBIA approach is novel in that it allows the classification of lakes regardless of the physical state of their water, and also allows the separation of frozen lakes from glaciers that have very similar water indices used in purely optical remote sensing applications. The algorithm proposed for snow avalanches allows the detection of release zones, tracks, and deposition zones by verifying the snow heterogeneity based on a roughness metric evaluated from a water index, and by analysing the local relation of segments with their neighbouring objects. This algorithm contains few steps, which allows for the simultaneous classification of avalanches that occur on diverse mountain slopes and differ in size and shape.
This thesis contributes to natural hazard research as it provides automatic solutions to tracking six different landforms that are diagnostic of natural hazards over large regions. This is a step toward delineating areas susceptible to the processes producing these landforms and the improvement of hazard maps.
In der vorliegenden Arbeit konnten erfolgreich zwei unterschiedliche Hybridmaterialien (HM) über die Sol-Gel-Methode synthetisiert werden. Bei den HM handelt es sich um Monolithe mit einem Durchmesser von bis zu 4,5 cm. Das erste HM besteht aus Titandioxid und Bombyx mori Seide und wird als TS bezeichnet, während das zweite weniger Seide und zusätzlich Polyethylenoxid (PEO) enthält und daher als TPS abgekürzt wird. Einige der HM wurden nach der Synthese in eine wässrige Tetrachloridogoldsäure-Lösung getaucht, wodurch sich auf der Oberfläche Goldnanopartikel gebildet haben.
Die Materialien wurden mittels Elektronenmikroskopie, energiedispersiver Röntgenspektroskopie, Ramanspektroskopie sowie Röntgenpulverdiffraktometrie charakterisiert. Die Ergebnisse zeigen, dass beide HM aus etwa 5 nm großen, sphärischen Titandioxidnanopartikeln aufgebaut sind, die primär aus Anatas und zu einem geringen Anteil aus Brookit bestehen. Die Goldnanopartikel bei TPS_Au waren größer und polydisperser als die Goldnanopartikel auf dem TS_Au HM. Darüber hinaus sind die Goldnanopartikel im TS HM tiefer in das Material eingedrungen als beim TPS HM.
Die weiterführende Analyse der HM mittels Elementaranalyse und thermogravimetrischer Analyse ergab für TPS einen geringeren Anteil an organischen Bestandteilen im HM als für TS, obwohl für beide Synthesen die gleiche Masse an organischen Materialien eingesetzt wurde. Es wird vermutet, dass das PEO während der Synthese teilweise wieder aus dem Material herausgewaschen wird. Diese Theorie korreliert mit den Ergebnissen aus der Stickstoffsorption und der Quecksilberporosimetrie, die für das TPS HM eine höhere Oberfläche als für das TS HM anzeigten.
Die Variation einiger Syntheseparameter wie die Menge an Seide und PEO oder die Zusammensetzung der Titandioxidvorläuferlösung hatte einen großen Einfluss auf die synthetisierten HM. Während unterschiedliche Mengen an PEO die Größe des HM beeinflussten, konnte ohne Seide kein HM in einer ähnlichen Größe hergestellt werden. Die Bildung der HM wird stark von der Zusammensetzung der Titandioxidvorläuferlösung beeinflusst. Eine Veränderung führte daher nur selten zur Bildung eines homogenen HM.
Die in dieser Arbeit synthetisierten HM wurden als Photokatalysatoren für die Wasserspaltung und den Abbau von Methylenblau eingesetzt. Bei der photokatalytischen Wasserspaltung wurde zunächst der Einfluss unterschiedlicher Goldkonzentrationen beim TPS HM auf die Wasserstoffausbeute untersucht. Die besten Ergebnisse wurden bei einer Menge von 2,5 mg Tetrachloridogoldsäure erhalten. Darüber hinaus wurde gezeigt, dass mit dem TPS HM eine deutlich höhere Menge an Wasserstoff gewonnen werden konnte als mit dem TS HM. Die Ursachen für die schlechtere Aktivität werden in der geringeren spezifischen Oberfläche, der unterschiedlichen Porenstruktur, dem höheren Anteil an Seide und besonders in der geringeren Größe und höheren Eindringtiefe der Goldnanopartikel vermutet. Darüber hinaus konnte mit einem höheren UV-Anteil in der Lichtquelle sowie durch die Zugabe von Ethanol als Opferreagenz eine Zunahme der Wasserstoffausbeute erzielt werden.
Bei dem Methylenblauabbau wurde für beide HM zunächst nur eine Adsorption des Methylenblaus beobachtet. Nach der Zugabe von Wasserstoffperoxid konnte nach 8 h bereits eine fast vollständige Oxidation des Methylenblaus unter sichtbarem Licht beobachtet werden. Die Ursache für die etwas höhere Aktivität von TPS gegenüber TS wird in der unterschiedlichen Porenstruktur und dem höheren Anteil an Seide im TS HM vermutet. Insgesamt zeigen beide HM eine gute photokatalytische Aktivität für den Abbau von Methylenblau im Vergleich zu den erhaltenen Werten aus der Literatur.
Carbohydrate-protein interactions are ubiquitous in nature. They provide the initial molecular contacts in many cell-cell processes as for example immune responses, signal transduction, egg fertilization and infection processes of pathogenic viruses and bacteria. Furthermore, bacteria themselves are infected by bacteriophages, viruses which can cause the bacterial lysis, but do not affect other hosts. The infection process of a bacteriophage involves the specific detection and binding of the bacterium, which can be based on a carbohydrate-protein interaction. The mechanism of specific detection of pathogenic bacteria can thereby be useful for the development of bacteria sensors in the food industry or for tools in diagnostics.
Bacteriophages of the Podoviridae family use tailspike proteins for the specific detection of enteritis causing bacteria as Escherichia coli, Salmonella spp. or Shigella flexneri. The tailspike protein provides the first contact by binding to the carbohydrate containing O-antigen part of lipopolysaccharide in the Gram-negative cell wall. After binding to O-antigen repeating units, the enzymatic activity of tailspike proteins leads to cleavage of the carbohydrate chains, which enables the bacteriophage to approach the bacterial surface for DNA injection. Tailspike proteins thereby exhibit a relatively low affinity to the oligosaccharide structures of O-antigen due to the necessary binding, cleavage and release cycle, compared for example to antibodies. In this work it was aimed to study the determinants that influence carbohydrate affinity in the extended TSP binding grooves. This is a prerequisite to design a high-affinity tailspike protein based bacteria sensor.
For this purpose the tailspike protein of the bacteriophage Sf6 (Sf6 TSP) was used, which specifically binds Shigella flexneri Y O-antigen with two tetrasaccharide repeating units at the intersubunits of the trimeric β-helix protein. The Sf6 TSP endorhamnosidase cleaves the O-antigen, which leads to an octasaccharide as the main product. The binding affinity of inactive Sf6 TSP towards polysaccharide was characterized by fluorescence titration experiments and surface plasmon resonance (SPR).
Moreover, cysteine mutations were introduced into the Sf6 TSP binding site for the covalent thiol-coupling of an environment-sensitive fluorescent label to obtain a sensor for Shigella flexneri Y based on TSP-O-antigen recognition. This sensor showed a more than 100 % amplitude increase of a visible light fluorescence upon the binding of a polysaccharide test solution. Improvements of the TSP sensor can be achieved by increasing the tailspike affinity towards the O-antigen. Therefore molecular dynamics simulations evaluating ligand flexibility, hydrogen bond occupancies and water network distributions were used for affinity prediction on the available cysteine mutants of Sf6 TSP. The binding affinities were experimentally analyzed by SPR. This combined computational and experimental set-up for the design of a high-affinity carbohydrate binding protein could successfully distinguish strongly increased and decreased affinities of single amino acid mutants.
A thermodynamically and structurally well characterized set of another tailspike protein HK620 TSP with high-affinity mutants was used to evaluate the influence of water molecules on binding affinity. The free enthalpy of HK620 TSP oligosaccharide complex formation thereby either derived from the replacement of a conserved water molecule or by immobilization of two water molecules upon ligand binding. Furthermore, the enthalpic and entropic contributions of water molecules in a hydrophobic binding pocket could be assigned by free energy calculations. The findings in this work can be helpful for the improvement of carbohydrate docking and carbohydrate binding protein engineering algorithms in the future.
Background and objectives: Age-related losses of lower extremity muscle strength/power and deficits in static and particularly dynamic balance are associated with impaired functional performance and the occurrence of falls. It has been shown that balance and resistance training have the potential to improve balance and muscle strength in healthy older adults. However, it is still open to debate how the effectiveness of balance and resistance training in older adults is influenced by different factors. This includes the role of trunk muscle strength, the comprehensive effects of combined balance and resistance training, and the role of exercise supervision. Therefore, the primary objectives of this doctoral thesis are to investigate the relationship between trunk muscle strength and balance performance and to examine the effects of an expert-based balance and resistance training protocol on various measures of balance and lower extremity muscle strength/power in older adults. Furthermore, the impact of supervised versus unsupervised balance and/or resistance training interventions in the elderly will be evaluated.
Methods: Healthy older adults aged 63-80 years were included in a cross-sectional study, a longitudinal study, and a meta-analysis (range group means meta-analysis: 65.3-81.1 years) registering balance and muscle strength/power performance. Different measures of balance (i.e., static/dynamic, proactive, reactive) were examined using clinical (e.g., Romberg test) and instrumented tests (e.g., 10 meter walking test on a sensor-equipped walkway). Isometric strength of the trunk muscles was assessed using instrumented trunk muscle strength apparatus and lower extremity dynamic muscle strength/power was examined using clinical tests (e.g., Chair Stand Test). Further, a combined balance and resistance training protocol was applied to examine training-induced effects on balance and muscle strength/power as well as the role of supervision in older adults.
Results: Findings revealed that measures of trunk muscle strength and static steady-state balance as well as specific measures of dynamic steady-state balance were significantly associated in the elderly (0.42 ≤ r ≤ 0.57). Combined balance and resistance training significantly improved older adults' static/dynamic steady-state (e.g., Romberg test; habitual gait speed), pro-active (e.g., Timed Up and Go Test), and reactive balance (e.g., Push and Release Test) as well as muscle strength/power (e.g., Chair Stand Test) (0.62 ≤ Cohen’s d ≤ 2.86; all p < 0.05). Supervised compared to unsupervised balance and/or resistance training was superior in enhancing older adults' balance and muscle strength/power performance regarding all observed outcome categories [longitudinal study: effects for the supervised group 0.26 ≤ d ≤ 2.86, effects for the unsupervised group 0.06 ≤ d ≤ 2.30; meta-analysis: all between-subject standardized mean differences (SMDbs) in favor of the supervised training programs 0.24-0.53]. The meta-analysis additionally showed larger effects in favor of supervised interventions when compared to completely unsupervised interventions (0.28 ≤ SMDbs ≤ 1.24). These effects in favor of the supervised programs faded when compared with studies that implemented a small amount of supervised sessions in their unsupervised interventions (−0.06 ≤ SMDbs ≤ 0.41).
Conclusions: Trunk muscle strength is associated with steady-state balance performance and may therefore be integrated in fall-preventive exercise interventions for older adults. The examined positive effects on a large number of important intrinsic fall risk factors (e.g., balance deficits, muscle weakness) imply that particularly the combination of balance and resistance training appears to be a feasible and effective exercise intervention for fall prevention. Owing to the beneficial effects of supervised compared to unsupervised interventions, supervised sessions should be integrated in fall-preventive balance and/or resistance training programs for older adults.
Der konsularische Schutz
(2017)
Anlässlich der Zunahme von Entführungen deutscher Staatsangehöriger im Ausland und des im Jahr 2009 ergangenen Urteils des Bundesverwaltungsgerichts zu diesem Thema legt die vorliegende Arbeit eine detaillierte und umfassende Analyse der Rechtsgrundlagen für die Gewährung konsularischen Schutzes durch die Auslandsvertretungen der Bundesrepublik Deutschland vor.
Das erste Kapitel beinhaltet eine detaillierte Darstellung der sich aus dem Völker-, Europa- und Verfassungsrecht sowie aus dem Konsulargesetz ergebenen staatlichen Handlungspflichten sowie möglicher damit einhergehender Individualansprüche auf die Ausübung konsularischen Schutzes im Einzelfall.
Im zweiten Kapitel werden die Voraussetzungen der Gewährung konsularischen Schutzes nach dem Konsulargesetz dargestellt. Den Schwerpunkt bildet hierbei die Bestimmung des Anwendungsbereiches des § 5 Abs. 1 Satz 1 Konsulargesetz unter Berücksichtigung des Urteils des Bundesverwaltungsgerichtes vom 28.05.2009, welches nach Auffassung der Verfasserin den Anwendungsbereich dieser Norm verkennt. Bei § 5 Abs. 1 Satz 1 Konsulargesetz handelt es sich um eine besondere sozialhilferechtliche Norm außerhalb der SGB XII, welche die konsularische Hilfe allein in wirtschaftlichen Notlagen regelt.
Das dritte Kapitel analysiert die bestehenden Regelungen über die Erstattung der im Rahmen der Gewährung konsularischen Schutzes entstandenen Kosten und erklärt deren Systematik. Ferner erfolgt ein Ausblick auf die künftigen Regelungen der Kostenerstattung nach dem Bundesgebührengesetz sowie der damit einhergehenden Rechtsverordnung.
Zum Abschluss werden die Ergebnisse anhand eines historischen Falles zusammengefasst sowie ein Gesetzesvorschlag vorgestellt, welcher die gefundenen Unklarheiten und Unstimmigkeiten im Konsulargesetz beheben kann.
We present electrical impedance measurements of amoeboid cells on microelectrodes. The model organism Dictyostelium discoideum shows under starvation conditions a transition to collective behavior when chemotactic cells collect in multicellular aggregates. We show how impedance recordings give a precise picture of the stages of aggregation by tracing the dynamics of cell-substrate adhesion. Furthermore, we present for the first time systematic single cell measurements of wild type cells and four mutant strains that differ in their substrate adhesion strength. We recorded the projected cell area by time lapse microscopy and found a correlation between quasi-periodic oscillations in the kinetics of the projected area - the cell shape oscillation - and the long-term trend in the impedance signal. Typically, amoeboid motility advances via a cycle of membrane protrusion, substrate adhesion, traction of the cell body and tail retraction. This motility cycle results in the quasi-periodic oscillations of the projected cell area and the impedance. In all cell lines measured, similar periods were observed for this cycle, despite the differences in attachment strength. We observed that cell-substrate attachment strength strongly affects the impedance in that the deviations from mean (the magnitude of fluctuations) are enhanced in cells that effectively transmit forces, generated by the cytoskeleton, to the substrate. For example, in talA- cells, which lack the actin anchoring protein talin, the fluctuations are strongly reduced. Single cell force spectroscopy and results from a detachment assay, where adhesion is measured by exposing cells to shear stress, confirm that the magnitude of impedance fluctuations is a correct measure for the strength of substrate adhesion. Finally, we also worked on the integration of cell-substrate impedance sensors into microfluidic devices. A chip-based electrical chemotaxis assay is designed which measures the speed of chemotactic cells migrating over microelectrodes along a chemical concentration gradient.
Adipositas wird mit einer Vielzahl schwerwiegender Folgeerkrankungen in Verbindung gebracht. Eine Gewichtsreduktion führt zu einer Verbesserung der metabolischen Folgen der Adipositas. Es ist bekannt, dass die Mehrzahl der adipösen Personen in den Monaten nach der Gewichtsreduktion einen Großteil des abgenommenen Gewichts wieder zunimmt. Nichtsdestotrotz existiert eine hohe Variabilität hinsichtlich des Langzeiterfolges einer Gewichtsreduktion. Der erfolgreiche Erhalt des reduzierten Körpergewichts einiger Personen führt zu der Frage nach den Faktoren, die einen Gewichtserhalt beeinflussen, mit dem Ziel einen Ansatzpunkt für mögliche Therapiestrategien zu identifizieren.
In der vorliegenden Arbeit wurde im Rahmen einer kontrollierten, randomisierten Studie mit 143 übergewichtigen Probanden untersucht, ob nach einer dreimonatigen Gewichtsreduktion eine zwölfmonatige gewichtsstabilisierende Lebensstilintervention einen Einfluss auf die Veränderungen der neuroendokrinen Regelkreisläufe und damit auf den langfristigen Gewichtserhalt über einen Zeitraum von achtzehn Monaten hat.
Hierbei wurde im Vergleich der beiden Behandlungsgruppen primär festgestellt, dass die multimodale Lebensstilintervention zu einer Gewichtstabilisierung über die Dauer dieser zwölfmonatigen Behandlungsphase führte. In der Kontrollgruppe kam es zu einer moderaten Gewichtszunahme . Dadurch war nach Beendigung der Interventionsphase der BMI der Teilnehmer in der Kontrollgruppe höher als der in der Interventionsgruppe (34,1±6,0 kg*m-2 vs. 32,4±5,7 kg*m-2; p<0,01).
Während der Nachbeobachtungszeit war die Interventionsgruppe durch eine signifikant stärkere Gewichtswiederzunahme im Vergleich zur Kontrollgruppe gekennzeichnet, so dass der BMI zwischen beiden Behandlungsgruppen bereits sechs Monate nach der Intervention keinen Unterschied mehr aufwies.
Bezüglich der hormonellen Veränderung durch die Gewichtsreduktion wurde, wie erwartet, eine Auslenkung des endokrinen Systems beobachtet. Jedoch konnte kein Unterschied der untersuchten Hormone im Vergleich der beiden Behandlungsgruppen ausfindig gemacht werden.
Im Verlauf der Gewichtsabnahme und der anschließenden Studienphasen zeigten sich tendenziell drei verschiedene Verlaufsmuster in den hormonellen Veränderungen. Nach einer zusätzlichen Adjustierung auf den jeweiligen BMI des Untersuchungszeitpunktes konnte für die TSH-Spiegel (p<0,05), die Schilddrüsenhormone (p<0,001) und für die IGF 1-Spiegel (p<0,001) eine über die Studienzeit anhaltende Veränderung festgestellt werden.
Abschließend wurde behandlungsgruppenunabhängig untersucht, ob die Hormonspiegel nach Gewichtsreduktion oder ob die relative hormonelle Veränderung während der Gewichtsreduktion prädiktiv für den Erfolg der Gewichterhaltungsphase ist. Hier fand sich für die Mehrzahl der hormonellen Parameter kein Effekt auf die Langzeitentwicklung der Gewichtszunahme. Jedoch konnte gezeigt werden, dass eine geringere Abnahme der 24h Urin-Metanephrin-Ausscheidung während der Gewichtsabnahmephase mit einem besseren Erfolg bezüglich des Gewichtserhalts über die achtzehnmonatige Studienzeit assoziiert war (standardisiertes Beta= -0,365; r2=0,133 p<0,01). Die anderen hormonellen Achsen zeigten keinen nachweislichen Effekt.
The Cauchy problem for the linearised Einstein equation and the Goursat problem for wave equations
(2017)
In this thesis, we study two initial value problems arising in general relativity. The first is the Cauchy problem for the linearised Einstein equation on general globally hyperbolic spacetimes, with smooth and distributional initial data. We extend well-known results by showing that given a solution to the linearised constraint equations of arbitrary real Sobolev regularity, there is a globally defined solution, which is unique up to addition of gauge solutions. Two solutions are considered equivalent if they differ by a gauge solution. Our main result is that the equivalence class of solutions depends continuously on the corre- sponding equivalence class of initial data. We also solve the linearised constraint equations in certain cases and show that there exist arbitrarily irregular (non-gauge) solutions to the linearised Einstein equation on Minkowski spacetime and Kasner spacetime.
In the second part, we study the Goursat problem (the characteristic Cauchy problem) for wave equations. We specify initial data on a smooth compact Cauchy horizon, which is a lightlike hypersurface. This problem has not been studied much, since it is an initial value problem on a non-globally hyperbolic spacetime. Our main result is that given a smooth function on a non-empty, smooth, compact, totally geodesic and non-degenerate Cauchy horizon and a so called admissible linear wave equation, there exists a unique solution that is defined on the globally hyperbolic region and restricts to the given function on the Cauchy horizon. Moreover, the solution depends continuously on the initial data. A linear wave equation is called admissible if the first order part satisfies a certain condition on the Cauchy horizon, for example if it vanishes. Interestingly, both existence of solution and uniqueness are false for general wave equations, as examples show. If we drop the non-degeneracy assumption, examples show that existence of solution fails even for the simplest wave equation. The proof requires precise energy estimates for the wave equation close to the Cauchy horizon. In case the Ricci curvature vanishes on the Cauchy horizon, we show that the energy estimates are strong enough to prove local existence and uniqueness for a class of non-linear wave equations. Our results apply in particular to the Taub-NUT spacetime and the Misner spacetime. It has recently been shown that compact Cauchy horizons in spacetimes satisfying the null energy condition are necessarily smooth and totally geodesic. Our results therefore apply if the spacetime satisfies the null energy condition and the Cauchy horizon is compact and non-degenerate.
In the present work side-chain polystyrenes were synthesized and characterized, in order to be applied in multilayer OLEDs fabricated by solution process techniques. Manufacture of optoelectronic devices by solution process techniques is meant to decrease significantly fabrication cost and allow large scale production of such devices.
This dissertation focusses in three series, enveloped in two material classes. The two classes differ to each other in the type of charge transport exhibited, either ambipolar transport or electron transport. All materials were applied in all-organic solution processed green Ir-based devices.
In the first part, a series of ambipolar host materials were developed to transport both charge types, holes and electrons, and be applied especially as matrix for green Ir-based emitters. It was possible to increase devices efficacy by modulating the predominant charge transport type. This was achieved by modification of molecules electron transport part with more electron-deficient heterocycles or by extending the delocalization of the LUMO. Efficiencies up to 28.9 cd/A were observed for all-organic solution-process three layer devices.
In the second part, suitability of triarylboranes and tetraphenylsilanes as electron transport materials was studied. High triplet energies were obtained, up to 2.95 eV, by rational combination of both molecular structures. Although the combination of both elements had a low effect in materials electron transport properties, high efficiencies around 24 cd/A were obtained for the series in all-organic solution-processed two layer devices.
In the last part, benzene and pyridine were chosen as the series electron-transport motif. By controlling the relative pyridine content (RPC) solubility into methanol was induced for polystyrenes with bulky side-chains. Materials with RPC ≥ 0.5 could be deposited orthogonally from solution without harming underlying layers. From the best of our knowledge, this is the first time such materials are applied in this architecture showing moderate efficiencies around 10 cd/A in all-organic solution processed OLEDs.
Overall, the outcome of these studies will actively contribute to the current research on materials for all-solution processed OLEDs.
Direct anthropogenic influences on the Earth’s subsurface during drilling, extraction or injection activities, can affect land stability by causing subsidence, uplifts or lateral displacements. They can occur in localized as well as in uninhabited and inhabited regions. Thus the associated risks for humans, infrastructure, and environment must be minimized. To achieve this, appropriate surveillance methods must be found that can be used for simultaneous monitoring during such activities. Multi-temporal synthetic aperture radar interferometry (MT-InSAR) methods like the Persistent Scatterer Interferometry (PSI) and the Small BAseline Subsets (SBAS) have been developed as standard approaches for satellite-based surface displacement monitoring. With increasing spatial resolution and availability of SAR sensors in recent years, MT-InSAR can be valuable for the detection and mapping of even the smallest man-made displacements.
This doctoral thesis aims at investigating the capacities of the mentioned standard methods for this purpose, and comprises three main objectives against the backdrop of a user-friendly surveillance service:
(1) the spatial and temporal significance assessment against leveling, (2) the suitability evaluation of PSI and SBAS under different conditions, and (3) the analysis of the link between surface motion and subsurface processes.
Two prominent case studies on anthropogenic induced subsurface processes in Germany serve as the basis for this goal. The first is the distinct urban uplift with severe damages at Staufen im Breisgau that has been associated since 2007 with a failure to implement a shallow geothermal energy supply for an individual building. The second case study considers the pilot project of geological carbon dioxide (CO2) storage at Ketzin, and comprises borehole drilling and fluid injection of more than 67 kt CO2 between 2008 and 2013. Leveling surveys at Staufen and comprehensive background knowledge of the underground processes gained from different kinds of in-situ measurements at both locations deliver a suitable basis for this comparative study and the above stated objectives. The differences in location setting, i.e. urban versus rural site character, were intended to investigate the limitations in the applicability of PSI and SBAS.
For the MT-InSAR analysis, X-band images from the German TerraSAR-X and TanDEM-X satellites were acquired in the standard Stripmap mode with about 3 m spatial resolution in azimuth and range direction. Data acquisition lasted over a period of five years for Staufen (2008-2013), and four years for Ketzin (2009-2013). For the first approximation of the subsurface source, an inversion of the InSAR outcome in Staufen was applied. The modeled uplift based on complex hydromechanical simulations and a correlation analysis with bottomhole pressure data were used for comparison with MT-InSAR measurements at Ketzin.
In response to the defined objectives of this thesis, a higher level of detail can be achieved in mapping surface displacements without in-situ effort by using MT-InSAR in comparison to leveling (1). A clear delineation of the elliptical shaped uplift border and its magnitudes at different parts was possible at Staufen, with the exception of a vegetated area in the northwest. Vegetation coverage and the associated temporal signal decorrelation are the main limitations of MT-InSAR as clearly demonstrated at the Ketzin test site. They result in insufficient measurement point density and unwrapping issues. Therefore, spatial resolutions of one meter or better are recommended to achieve an adequate point density for local displacement analysis and to apply signal noise reduction. Leveling measurements can provide a complementary data source here, but require much effort pertaining to personnel even at the local scale. Horizontal motions could be identified at Staufen by only comparing the temporal evolution of the 1D line of sight (LOS) InSAR measurements with the available leveling data. An exception was the independent LOS decomposition using ascending and descending data sets for the period 2012-2013. The full 3D displacement field representation failed due to insufficient orbit-related, north-south sensitivity of the satellite-based measurements. By using the dense temporal mapping capabilities of the TerraSAR-X/TanDEM-X satellites after every 11 days, the temporal displacement evolution could be captured as good as that with leveling.
With respect to the tested methods and in the view of generality, SBAS should be preferred over PSI (2). SBAS delivered a higher point density, and was therefore less affected by phase unwrapping issues in both case studies. Linking surface motions with subsurface processes is possible when considering simplified geophysical models (3), but it still requires intensive research to gain a deep understanding.
The goal of this thesis is related to the question how to introduce and combine simultaneously plasmonic and photoswitching properties to different nano-objects. In this thesis I investigate the complexes between noble metal nanoparticles and cationic surfactants containing azobenzene units in their hydrophobic tail, employing absorption spectroscopy, surface zeta-potential, and electron microscopy.
In the first part of the thesis, the formation of complexes between negatively charged laser ablated spherical gold nanoparticles and cationic azobenzene surfactants in trans- conformation is explored. It is shown that the constitution of the complexes strongly depends on a surfactant-to-gold molar ratio. At certain molar ratios, particle self-assembly into nanochains and their aggregation have been registered. At higher surfactant concentrations, the surface charge of nanoparticles turned positive, attributed to the formation of the stabilizing double layer of azobenzene surfactants on gold nanoparticle surfaces. These gold-surfactant complexes remained colloidally stable. UV light induced trans-cis isomerization of azobenzene surfactant molecules and thus perturbed the stabilizing surfactant shell, causing nanoparticle aggregation. The results obtained with silver and silicon nanoparticles mimick those for the comprehensively studied gold nanoparticles, corroborating the proposed model of complex formation.
In the second part, the interaction between plasmonic metal nanoparticles (Au, Ag, Pd, alloy Au-Ag, Au-Pd), as well as silicon nanoparticles, and cis-isomers of azobenzene containing compounds is addressed. Cis-trans thermal isomerization of azobenzenes was enhanced in the presence of gold, palladium, and alloy gold-palladium nanoparticles. The influence of the surfactant structure and nanoparticle material on the azobenzene isomerization rate is expounded. Gold nanoparticles showed superior catalytic activity for thermal cis-trans isomerization of azobenzenes. In a joint project with theoretical chemists, we demonstrated that the possible physical origin of this phenomenon is the electron transfer between azobenzene moieties and nanoparticle surfaces.
In the third part, complexes between gold nanorods and azobenzene surfactants with different tail length were exposed to UV and blue light, inducing trans-cis and cis-trans isomerization of surfactant, respectively. At the same time, the position of longitudinal plasmonic absorption maximum of gold nanorods experienced reversible shift responding to the changes in local dielectric environment. Surface plasmon resonance condition allowed the estimation of the refractive index of azobenzene containing surfactants in solution.
Persistently high unemployment rates are a major threat to the social cohesion in many societies. To moderate the consequences of unemployment industrialized countries spend substantial shares of their GDP on labor market policies, while in recent years there has been a shift from passive measures, such as transfer payments, towards more activating elements which aim to promote the reintegration into the labor market. Although, there exists a wide range of evidence about the effects of traditional active labor market policies (ALMP) on participants’ subsequent labor market outcomes, a deeper understanding of the impact of these programs on the job search behavior and the interplay with long-term labor market outcomes is necessary. This allows policy makers to improve the design of labor market policies and the allocation of unemployed workers into specific programs. Moreover, previous studies have shown that many traditional ALMP programs, like public employment or training schemes, do not achieve the desired results. This underlines the importance of understanding the effect mechanisms, but also the need to develop innovative programs that are more effective. This thesis extends the existing literature with respect to several dimensions.
First, it analyzes the impact of job seekers’ beliefs about upcoming ALMPs programs on the effectiveness of realized treatments later during the unemployment spell. This provides important insights with respect to the job search process and relates potential anticipation effects (on the job seekers behavior before entering a program) to the vast literature evaluating the impact of participating in an ALMP program on subsequent outcomes. The empirical results show that training programs are more effective if the participants expect participation ex ante, while expected treatment effects are unrelated to the actual labor market outcomes of participants. A subsequent analysis of the effect mechanisms shows that job seekers who expect to participate also receive more information by their caseworker and show a higher willingness to adjust their search behavior in association with an upcoming ALMP program. The findings suggest that the effectiveness of training programs can be improved by providing more detailed information about the possibility of a future treatment early during the unemployment spell.
Second, the thesis investigates the effects of a relatively new class of programs that aim to improve the geographical mobility of unemployed workers with respect to the job search behavior, the subsequent job finding prospects and the returns to labor market mobility. To estimate the causal impact of these programs, it is exploited that local employment agencies have a degree of autonomy when deciding about the regional-specific policy mix. The findings show that the policy style of the employment agency indeed affects the job search behavior of unemployed workers. Job seekers who are assigned to agencies with higher preferences for mobility programs increase their search radius without affecting the total number of job applications. This shift of the search effort to distant regions leads to a higher probability to find a regular job and higher wages. Moreover, it is shown that participants in one of the subsidy programs who move to geographically distant region a earn significantly higher wages, end up in more stable jobs and face a higher long-run employment probability compared to non-participants.
Third, the thesis offers an empirical assessment of the unconfoundedness assumption with respect to the relevance of variables that are usually unobserved in studies evaluating ALMP programs. A unique dataset that combines administrative records and survey data allows us to observe detailed information on typical covariates, as well as usually unobserved variables including personality traits, attitudes, expectations, intergenerational information, as well as indicators about social networks and labor market flexibility. The findings show that, although our set of usually unobserved variables indeed has a significant effect on the selection into ALMP programs, the overall impact when estimating treatment effects is rather small.
Finally, the thesis also examines the importance of gender differences in reservation wages that allows assessing the importance of special ALMP programs targeting women. In particular, when including reservation wages in a wage decomposition exercise, the gender gap in realized wages becomes small and statistically insignificant. The strong connection between gender differences in reservation wages and realized wages raises the question how these differences in reservation wages are set in the first place. Since traditional covariates cannot sufficiently explain the gender gap in reservation wages, we perform subgroup analysis to better understand what the driving forces behind this gender gap are.
This cumulative dissertation consists of five chapters. In terms of research content, my thesis can be divided into two parts. Part one examines local interactions and spillover effects between small regional governments using spatial econometric methods. The second part focuses on patterns within municipalities and inspects which institutions of citizen participation, elections and local petitions, influence local housing policies.
Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes
(2017)
Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures.
In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges.
These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure.
Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67% of this specific capacitance when the scan rate is increased to 200 mV s-1.
In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking.
Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes.
Personal Big Data
(2017)
Many users of cloud-based services are concerned about questions of data privacy. At the same time, they want to benefit from smart data-driven services, which require insight into a person’s individual behaviour. The modus operandi of user modelling is that data is sent to a remote server where the model is constructed and merged with other users’ data. This thesis proposes selective cloud computing, an alternative approach, in which the user model is constructed on the client-side and only an abstracted generalised version of the model is shared with the remote services.
In order to demonstrate the applicability of this approach, the thesis builds an exemplary client-side user modelling technique. As this thesis is carried out in the area of Geoinformatics and spatio-temporal data is particularly sensitive, the application domain for this experiment is the analysis and prediction of a user’s spatio-temporal behaviour.
The user modelling technique is grounded in an innovative conceptual model, which builds upon spatial network theory combined with time-geography. The spatio-temporal constraints of time-geography are applied to the network structure in order to create individual spatio-temporal action spaces. This concept is translated into a novel algorithmic user modelling approach which is solely driven by the user’s own spatio-temporal trajectory data that is generated by the user’s smartphone.
While modern smartphones offer a rich variety of sensory data, this thesis only makes use of spatio-temporal trajectory data, enriched by activity classification, as the input and foundation for the algorithmic model. The algorithmic model consists of three basal components: locations (vertices), trips (edges), and clusters (neighbourhoods).
After preprocessing the incoming trajectory data in order to identify locations, user feedback is used to train an artificial neural network to learn temporal patterns for certain location types (e.g. work, home, bus stop, etc.). This Artificial Neural Network (ANN) is used to automatically detect future location types by their spatio-temporal patterns. The same is done in order to predict the duration of stay at a certain location. Experiments revealed that neural nets were the most successful statistical and machine learning tool to detect those patterns. The location type identification algorithm reached an accuracy of 87.69%, the duration prediction on binned data was less successful and deviated by an average of 0.69 bins. A challenge for the location type classification, as well as for the subsequent components, was the imbalance of trips and connections as well as the low accuracy of the trajectory data. The imbalance is grounded in the fact that most users exhibit strong habitual patterns (e.g. home > work), while other patterns are rather rare by comparison. The accuracy problem derives from the energy-saving location sampling mode, which creates less accurate results.
Those locations are then used to build a network that represents the user’s spatio-temporal behaviour. An initial untrained ANN to predict movement on the network only reached 46% average accuracy. Only lowering the number of included edges, focusing on more common trips, increased the performance. In order to further improve the algorithm, the spatial trajectories were introduced into the predictions. To overcome the accuracy problem, trips between locations were clustered into so-called spatial corridors, which were intersected with the user’s current trajectory. The resulting intersected trips were ranked through a k-nearest-neighbour algorithm. This increased the performance to 56%. In a final step, a combination of a network and spatial clustering algorithm was built in order to create clusters, therein reducing the variety of possible trips. By only predicting the destination cluster instead of the exact location, it is possible to increase the performance to 75% including all classes.
A final set of components shows in two exemplary ways how to deduce additional inferences from the underlying spatio-temporal data. The first example presents a novel concept for predicting the ‘potential memorisation index’ for a certain location. The index is based on a cognitive model which derives the index from the user’s activity data in that area. The second example embeds each location in its urban fabric and thereby enriches its cluster’s metadata by further describing the temporal-semantic activity in an area (e.g. going to restaurants at noon).
The success of the client-side classification and prediction approach, despite the challenges of inaccurate and imbalanced data, supports the claimed benefits of the client-side modelling concept. Since modern data-driven services at some point do need to receive user data, the thesis’ computational model concludes with a concept for applying generalisation to semantic, temporal, and spatial data before sharing it with the remote service in order to comply with the overall goal to improve data privacy. In this context, the potentials of ensemble training (in regards to ANNs) are discussed in order to highlight the potential of only sharing the trained ANN instead of the raw input data.
While the results of our evaluation support the assets of the proposed framework, there are two important downsides of our approach compared to server-side modelling. First, both of these server-side advantages are rooted in the server’s access to multiple users’ data. This allows a remote service to predict spatio-in the user-specific data, which represents the second downside. While minor classes will likely be minor classes in a bigger dataset as well, for each class, there will still be more variety than in the user-specific dataset. The author emphasises that the approach presented in this work holds the potential to change the privacy paradigm in modern data-driven services. Finding combinations of client- and server-side modelling could prove a promising new path for data-driven innovation.
Beyond the technological perspective, throughout the thesis the author also offers a critical view on the data- and technology-driven development of this work. By introducing the client-side modelling with user-specific artificial neural networks, users generate their own algorithm. Those user-specific algorithms are influenced less by generalised biases or developers’ prejudices. Therefore, the user develops a more diverse and individual perspective through his or her user model. This concept picks up the idea of critical cartography, which questions the status quo of how space is perceived and represented.
Borehole instabilities are frequently encountered when drilling through finely laminated, organic rich shales (Økland and Cook, 1998; Ottesen, 2010; etc.); such instabilities should be avoided to assure a successful exploitation and safe production of the contained unconventional hydrocarbons. Borehole instabilities, such as borehole breakouts or drilling induced tensile fractures, may lead to poor cementing of the borehole annulus, difficulties with recording and interpretation of geophysical logs, low directional control and in the worst case the loss of the well. If these problems are not recognized and expertly remedied, pollution of the groundwater or the emission of gases into the atmosphere can occur since the migration paths of the hydrocarbons in the subsurface are not yet fully understood (e.g., Davies et al., 2014; Zoback et al., 2010). In addition, it is often mentioned that the drilling problems encountered and the resulting downtimes of the wellbore system in finely laminated shales significantly increase drilling costs (Fjaer et al., 2008; Aadnoy and Ong, 2003).
In order to understand and reduce the borehole instabilities during drilling in unconventional shales, we investigate stress-induced irregular extensions of the borehole diameter, which are also referred to as borehole breakouts. For this purpose, experiments with different borehole diameters, bedding plane angles and stress boundary conditions were performed on finely laminated Posidonia shales. The Lower Jurassic Posidonia shale is one of the most productive source rocks for conventional reservoirs in Europe and has the greatest potential for unconventional oil and gas in Europe (Littke et al., 2011).
In this work, Posidonia shale specimens from the North (PN) and South (PS) German basins were selected and characterized petrophysically and mechanically. The composition of the two shales is dominated by calcite (47-56%) followed by clays (23-28%) and quartz (16-17%). The remaining components are mainly pyrite and organic matter. The porosity of the shales varies considerably and is up to 10% for PS and 1% for PN, which is due to a larger deposition depth of PN. Both shales show marked elasticity and strength anisotropy, which can be attributed to a macroscopic distribution and orientation of soft and hard minerals. Under load the hard minerals form a load-bearing, supporting structure, while the soft minerals compensate the deformation. Therefore, if loaded parallel to the bedding, the Posidonia shale is more brittle than loaded normal to the bedding. The resulting elastic anisotropy, which can be defined by the ratio of the modulus of elasticity parallel and normal to the bedding, is about 50%, while the strength anisotropy (i.e., the ratio of uniaxial compressive strength normal and parallel to the bedding) is up to 66%. Based on the petrophysical characterization of the two rocks, a transverse isotropy (TVI) was derived. In general, PS is softer and weaker than PN, which is due to the stronger compaction of the material due to the higher burial depth.
Conventional triaxial borehole breakout experiments on specimens with different borehole diameters showed that, when the diameter of the borehole is increased, the stress required to initiate borehole breakout decreases to a constant value. This value can be expressed as the ratio of the tangential stress and the uniaxial compressive strength of the rock. The ratio increases exponentially with decreasing borehole diameter from about 2.5 for a 10 mm diameter hole to ~ 7 for a 1 mm borehole (increase of initiation stress by 280%) and can be described by a fracture mechanic based criterion. The reduction in borehole diameter is therefore a considerable aspect in reducing the risk of breakouts. New drilling techniques with significantly reduced borehole diameters, such as "fish-bone" holes, are already underway and are currently being tested (e.g., Xing et al., 2012).
The observed strength anisotropy and the TVI material behavior are also reflected in the observed breakout processes at the borehole wall. Drill holes normal to the bedding develop breakouts in a plane of isotropy and are not affected by the strength or elasticity anisotropy. The observed breakouts are point-symmetric and form compressive shear failure planes, which can be predicted by a Mohr-Coulomb failure approach. If the shear failure planes intersect, conjugate breakouts can be described as "dog-eared” breakouts.
While the initiation of breakouts for wells oriented normal to the stratification has been triggered by random local defects, reduced strengths parallel to bedding planes are the starting point for breakouts for wells parallel to the bedding. In the case of a deflected borehole trajectory, therefore, the observed failure type changes from shear-induced failure surfaces to buckling failure of individual layer packages. In addition, the breakout depths and widths increased, resulting in a stress-induced enlargement of the borehole cross-section and an increased output of rock material into the borehole. With the transition from shear to buckling failure and changing bedding plane angle with respect to the borehole axis, the stress required for inducing wellbore breakouts drops by 65%.
These observations under conventional triaxial stress boundary conditions could also be confirmed under true triaxial stress conditions. Here breakouts grew into the rock as a result of buckling failure, too. In this process, the broken layer packs rotate into the pressure-free drill hole and detach themselves from the surrounding rock by tensile cracking. The final breakout shape in Posidonia shale can be described as trapezoidal when the bedding planes are parallel to the greatest horizontal stress and to the borehole axis. In the event that the largest horizontal stress is normal to the stratification, breakouts were formed entirely by shear fractures between the stratification and required higher stresses to initiate similar to breakouts in conventional triaxial experiments with boreholes oriented normal to the bedding.
In the content of this work, a fracture mechanics-based failure criterion for conventional triaxial loading conditions in isotropic rocks (Dresen et al., 2010) has been successfully extended to true triaxial loading conditions in the transverse isotropic rock to predict the initiation of borehole breakouts. The criterion was successfully verified on the experiments carried out.
The extended failure criterion and the conclusions from the laboratory and numerical work may help to reduce the risk of borehole breakouts in unconventional shales.
Development of a reliable and environmentally friendly synthesis for fluorescence carbon nanodots
(2017)
Carbon nanodots (CNDs) have generated considerable attention due to their promising properties, e.g. high water solubility, chemical inertness, resistance to photobleaching, high biocompatibility and ease of functionalization. These properties render them ideal for a wide range of functions, e.g. electrochemical applications, waste water treatment, (photo)catalysis, bio-imaging and bio-technology, as well as chemical sensing, and optoelectronic devices like LEDs. In particular, the ability to prepare CNDs from a wide range of accessible organic materials makes them a potential alternative for conventional organic dyes and semiconductor quantum dots (QDs) in various applications. However, current synthesis methods are typically expensive and depend on complex and time-consuming processes or severe synthesis conditions and toxic chemicals. One way to reduce overall preparation costs is the use of biological waste as starting material. Hence, natural carbon sources such as pomelo peal, egg white and egg yolk, orange juice, and even eggshells, to name a few; have been used for the preparation of CNDs. While the use of waste is desirable, especially to avoid competition with essential food production, most starting-materials lack the essential purity and structural homogeneity to obtain homogeneous carbon dots. Furthermore, most synthesis approaches reported to date require extensive purification steps and have resulted in carbon dots with heterogeneous photoluminescent properties and indefinite composition. For this reason, among others, the relationship between CND structure (e.g. size, edge shape, functional groups and overall composition) and photophysical properties is yet not fully understood. This is particularly true for carbon dots displaying selective luminescence (one of their most intriguing properties), i.e. their PL emission wavelength can be tuned by varying the excitation wavelength.
In this work, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain CNDs with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch, carboxylic acids and Tris-EDTA (TE) buffer as carbon- and nitrogen source, respectively. The presented microwave-assisted hydrothermal precursor carbonization (MW-hPC) is characterized by its cost-efficiency, simplicity, short reaction times, low environmental footprint, and high yields of approx. 80% (w/w). Furthermore, only a single synthesis step is necessary to obtain homogeneous water-soluble CNDs with no need for further purification.
Depending on starting materials and reaction conditions different types of CNDs have been prepared. The as-prepared CNDs exhibit reproducible, highly homogeneous and favourable PL properties with narrow emission bands (approx. 70nm FWHM), are non-blinking, and are ready to use without need for further purification, modification or surface passivation agents. Furthermore, the CNDs are comparatively small (approx. 2.0nm to 2.4nm) with narrow size distributions; are stable over a long period of time (at least one year), either in solution or as a dried solid; and maintain their PL properties when re-dispersed in solution. Depending on CND type, the PL quantum yield (PLQY) can be adjusted from as low as 1% to as high as 90%; one of the highest reported PLQY values (for CNDs) so far.
An essential part of this work was the utilization of a microwave synthesis reactor, allowing various batch sizes and precise control over reaction temperature and -time, pressure, and heating- and cooling rate, while also being safe to operate at elevated reaction conditions (e.g. 230 ±C and 30 bar). The hereby-achieved high sample throughput allowed, for the first time, the thorough investigation of a wide range of synthesis parameters, providing valuable insight into the CND formation. The influence of carbon- and nitrogen source, precursor concentration and -combination, reaction time and -temperature, batch size, and post-synthesis purification steps were carefully investigated regarding their influence on the optical properties of as-synthesized CNDs. In addition, the change in photophysical properties resulting from the conversion of CND solution into solid and back into the solution was investigated. Remarkably, upon freeze-drying the initial brown CND-solution turns into a non-fluorescent white/slightly yellow to brown solid which recovers PL in aqueous solution. Selected CND samples were also subject to EDX, FTIR, NMR, PL lifetime (TCSPC), particle size (TEM), TGA and XRD analysis. Besides structural characterization, the pH- and excitation dependent PL characteristics (i.e. selective luminescence) were examined; giving inside into the origin of photophysical properties and excitation dependent behaviour of CNDs. The obtained results support the notion that for CNDs the nature of the surface states determines the PL properties and that excitation dependent behaviour is caused by the “Giant Red-Edge Excitation Shift” (GREES).
Im kognitiven Vulnerabilitäts-Stress-Modell der Depression von A.T. Beck (1967, 1976) spielen dysfunktionale Einstellungen bei der Entstehung von Depression in Folge von erlebtem Stress eine zentrale Rolle. Diese Theorie prägt seit Jahrzehnten die ätiologische Erforschung der Depression, jedoch ist die Bedeutung dysfunktionaler Einstellungen im Prozess der Entstehung einer Depression insbesondere im Kindes- und Jugendalter nach wie vor unklar. Die vorliegende Arbeit widmet sich einigen in der bisherigen Forschung wenig behandelten Fragen. Diese betreffen u. a. die Möglichkeit nichtlinearer Effekte dysfunktionaler Einstellungen, Auswirkungen einer Stichprobenselektion, Entwicklungseffekte sowie die Spezifität etwaiger Zusammenhänge für eine depressive Symptomatik.
Zur Beantwortung dieser Fragen wurden Daten von zwei Messzeitpunkten der PIER-Studie, eines großangelegten Längsschnittprojekts über Entwicklungsrisiken im Kindes- und Jugendalter, genutzt. Kinder und Jugendliche im Alter von 9 bis 18 Jahren berichteten zweimal im Abstand von ca. 20 Monaten im Selbstberichtsverfahren über ihre dysfunktionalen Einstellungen, Symptome aus verschiedenen Störungsbereichen sowie über eingetretene Lebensereignisse.
Die Ergebnisse liefern Evidenz für ein Schwellenmodell, in dem dysfunktionale Einstellungen unabhängig von Alter und Geschlecht nur im höheren Ausprägungsbereich eine Wirkung als Vulnerabilitätsfaktor zeigen, während im niedrigen Ausprägungsbereich keine Zusammenhänge zur späteren Depressivität bestehen. Eine Wirkung als Vulnerabilitätsfaktor war zudem nur in der Subgruppe der anfänglich weitgehend symptomfreien Kinder und Jugendlichen zu beobachten. Das Schwellenmodell erwies sich als spezifisch für eine depressive Symptomatik, es zeigten sich jedoch auch (teilweise ebenfalls nichtlineare) Effekte dysfunktionaler Einstellungen auf die Entwicklung von Essstörungssymptomen und aggressivem Verhalten. Bei 9- bis 13-jährigen Jungen standen dysfunktionale Einstellungen zudem in Zusammenhang mit einer Tendenz, Stress in Leistungskontexten herbeizuführen.
Zusammen mit den von Sahyazici-Knaak (2015) berichteten Ergebnissen aus der PIER-Studie weisen die Befunde darauf hin, dass dysfunktionale Einstellungen im Kindes- und Jugendalter – je nach betrachteter Subgruppe – Ursache, Symptom und Konsequenz der Depression darstellen können. Die in der vorliegenden Arbeit gezeigten nichtlinearen Effekte dysfunktionaler Einstellungen und die Effekte der Stichprobenselektion bieten eine zumindest teilweise Erklärung für die Heterogenität früherer Forschungsergebnisse. Insgesamt lassen sie auf komplexe – und nicht ausschließlich negative – Auswirkungen dysfunktionaler Einstellungen schließen. Für eine adäquate Beurteilung der „Dysfunktionalität“ der von A.T. Beck so betitelten Einstellungen erscheint daher eine Berücksichtigung der betrachteten Personengruppe, der absoluten Ausprägungen und der fraglichen Symptomgruppen geboten.
The classical Navier-Stokes equations of hydrodynamics are usually written in terms of vector analysis. More promising is the formulation of these equations in the language of differential forms of degree one. In this way the study of Navier-Stokes equations includes the analysis of the de Rham complex. In particular, the Hodge theory for the de Rham complex enables one to eliminate the pressure from the equations. The Navier-Stokes equations constitute a parabolic system with a nonlinear term which makes sense only for one-forms. A simpler model of dynamics of incompressible viscous fluid is given by Burgers' equation. This work is aimed at the study of invariant structure of the Navier-Stokes equations which is closely related to the algebraic structure of the de Rham complex at step 1. To this end we introduce Navier-Stokes equations related to any elliptic quasicomplex of first order differential operators. These equations are quite similar to the classical Navier-Stokes equations including generalised velocity and pressure vectors. Elimination of the pressure from the generalised Navier-Stokes equations gives a good motivation for the study of the Neumann problem after Spencer for elliptic quasicomplexes. Such a study is also included in the work.We start this work by discussion of Lamé equations within the context of elliptic quasicomplexes on compact manifolds with boundary. The non-stationary Lamé equations form a hyperbolic system. However, the study of the first mixed problem for them gives a good experience to attack the linearised Navier-Stokes equations. On this base we describe a class of non-linear perturbations of the Navier-Stokes equations, for which the solvability results still hold.
Galaxies evolve on cosmological timescales and to study this evolution we can either study the stellar populations, tracing the star formation and chemical enrichment, or the dynamics, tracing interactions and mergers of galaxies as well as accretion. In the last decades this field has become one of the most active research areas in modern astrophysics and especially the use of integral field spectrographs furthered our understanding. This work is based on data of NGC 5102 obtained with the panoramic integral field spectrograph MUSE. The data are analysed with two separate and complementary approaches: In the first part, standard methods are used to measure the kinematics and than model the gravitational potential using these exceptionally high-quality data. In the second part I develop the new method of surface brightness fluctuation spectroscopy and quantitatively explore its potential to investigate the bright evolved stellar population.
Measuring the kinematics of NGC 5102 I discover that this low-luminosity S0 galaxy hosts two counter rotating discs. The more central stellar component co-rotates with the large amount of HI gas. Investigating the populations I find strong central age and metallicity gradients with a younger and more metal rich central population. The spectral resolution of MUSE does not allow to connect these population gradients with the two counter rotating discs.
The kinematic measurements are modelled with Jeans anisotropic models to infer the gravitational potential of NGC 5102. Under the self-consistent mass-follows-light assumption none of the Jeans models is able to reproduce the observed kinematics. To my knowledge this is the strongest evidence evidence for a dark matter dominated system obtained with this approach so far. Including a Navarro, Frenk & White dark matter halo immediately solves the discrepancies. A very robust result is the logarithmic slope of the total matter density. For this low-mass galaxy I find a value of -1.75 +- 0.04, shallower than an isothermal halo and even shallower than published values for more massive galaxies. This confirms a tentative relation between total mass slope and stellar mass of galaxies.
The Surface Brightness Fluctuation (SBF) method is a well established distance measure, but due to its sensitive to bright stars also used to study evolved stars in unresolved stellar populations. The wide-field spectrograph MUSE offers the possibility to apply this technique for the first time to spectroscopic data. In this thesis I develop the spectroscopic SBF technique and measure the first SBF spectrum of any galaxy. I discuss the challenges for measuring SBF spectra that rise due to the complexity of integral field spectrographs compared to imaging instruments.
Since decades, stellar population models indicate that SBFs in intermediate-to-old stellar systems are dominated by red giant branch and asymptotic giant branch stars. Especially the later carry significant model uncertainties, making these stars a scientifically interesting target. Comparing the NGC 5102 SBF spectrum with stellar spectra I show for the first time that M-type giants cause the fluctuations. Stellar evolution models suggest that also carbon rich thermally pulsating asymptotic giant branch stars should leave a detectable signal in the SBF spectrum. I cannot detect a significant contribution from these stars in the NGC 5102 SBF spectrum.
I have written a stellar population synthesis tool that predicts for the first time SBF spectra. I compute two sets of population models: based on observed and on theoretical stellar spectra. In comparing the two models I find that the models based on observed spectra predict weaker molecular features. The comparison with the NGC 5102 spectrum reveals that these models are in better agreement with the data.
Throughout all different socio-historical tensions undergone by the Latin American modernit(ies), the literary-historical production as well as the reflection on the topic - regional, national, supranational and/or continental – have been part of the critical and intellectual itinerary of very significant political and cultural projects, whose particular development allows the analysis of the socio-discursive dynamics fulfilled by the literary historiography in the search of a historical conscience and representation of the esthetic-literary processes.
In present literary and cultural Central American literary studies, the academic thought on the development of the literary historiography has given place to some works whose main objects of study involve a significant corpus of national literature histories published mainly in the 20th century, between the forties and the eighties. Although these studies differ greatly from the vast academic production undertaken by the literary critics in the last two decades, the field of research of the literary historiography in Central America has made a theoretical-methodological effort, as of the eighties and until now, to analyze the local literary-historical productions.
However, this effort was carried out more systematically in the last five years of the 20th century, within the Central American democratic transition and post-war context, when a national, supra national and transnational model of literary history was boosted. This gave place to the creation and launching of the project Hacia una Historia de las Literaturas Centroamericanas (HILCAS) at the beginning of the new millennium.
Given the ideological relevance which the literary historiography has played in the process of the historical formation of the Hispano-American States, and whose philological tradition has also had an impact in the various Central American nation states, the emergence of this historiographic project marks an important rupture in relation with the national paradigms, and it is also manifested in a movement of transition and tension with regard to the new cultural, comparative and transareal dynamics, which seek to understand the geographical, transnational, medial and transdisciplinary movements within which the esthetic narrative processes and the idea and formation of a critical Central American subject gain shape.
Taking this aspect into account, our study puts forward as its main hypothesis that the historiographic thought developed as a consequence of the project Hacia una Historia de las Literaturas Centroamericanas (HILCAS) constitutes a socio-discursive practice, which reflects the formation of a historic-literary conscience and of a critical intellectual subject, an emergence that takes place between the mid-nineties and the first decade of the 21st century.
In this respect, and taking as a basis the general purpose of this investigation indicated before, the main justification for our object of study consists of making the Central American historiographic reflection visible as a part of the epistemological and cultural changes shown by the Latin American historiographic thought, and from which a new way of conceptualization of the space, the coexistence and the historic conscience emerge with regard to the esthetic-literary practices and processes.
Based on the field and hypothesis stated before, the general purpose of this research is framed by the socio-discursive dimension fulfilled by the Latin American literary historiography, and it aims to analyze the Central American historical-literary thought developed between the second half of the nineties and the beginning of the first decade of the 21st century.
Import and decomposition of dissolved organic carbon in pre-dams of drinking water reservoirs
(2017)
Dissolved organic carbon (DOC) depicts a key component in the aquatic carbon cycle as well as for drinking water production from surface waters. DOC concentrations increased in water bodies of the northern hemisphere in the last decades, posing ecological consequences and water quality problems. Within the pelagic zone of lakes and reservoirs, the DOC pool is greatly affected by biological activity as DOC is simultaneously produced and decomposed. This thesis aimed for a conceptual understanding of organic carbon cycling and DOC quality changes under differing hydrological and trophic conditions. Further, the occurrence of aquatic priming was investigated, which has been proposed as a potential process facilitating the microbial decomposition of stable allochthonous DOC within the pelagic zone.
To study organic carbon cycling under different hydrological conditions, quantitative and qualitative investigations were carried out in three pre-dams of drinking water reservoirs exhibiting a gradient in DOC concentrations and trophic states. All pre-dams were mainly autotrophic in their epilimnia. Discharge and temperature were identified as the key factors regulating net production and respiration in the upper water layers of the pre-dams. Considerable high autochthonous production was observed during the summer season under higher trophic status and base flow conditions. Up to 30% of the total gained organic carbon was produced within the epilimnia. Consequently, this affected the DOC quality within the pre-dams over the year and enhanced characteristics of algae-derived DOC were observed during base flow in summer. Allochthonous derived DOC dominated at high discharges and oligotrophic conditions when production and respiration were low. These results underline that also small impoundments with typically low water residence times are hotspots of carbon cycling, significantly altering water quality in dependence of discharge conditions, temperature and trophic status. Further, it highlights that these factors need to be considered in future water management as increasing temperatures and altered precipitation patterns are predicted in the context of climate change.
Under base flow conditions, heterotrophic bacteria preferentially utilized older DOC components with a conventional radiocarbon age of 195-395 years before present (i.e. before 1950). In contrast, younger carbon components (modern, i.e. produced after 1950) were mineralized following a storm flow event. This highlights that age and recalcitrance of DOC are independent from each other. To assess the ages of the microbially consumed DOC, a simplified method was developed to recover the respired CO2 from heterotrophic bacterioplankton for carbon isotope analyses (13C, 14C). The advantages of the method comprise the operation of replicate incubations at in-situ temperatures using standard laboratory equipment and thus enabling an application in a broad range of conditions.
Aquatic priming was investigated in laboratory experiments during the microbial decomposition of two terrestrial DOC substrates (peat water and soil leachate). Thereby, natural phytoplankton served as a source of labile organic matter and the total DOC pool increased throughout the experiments due to exudation and cell lysis of the growing phytoplankton. A priming effect for both terrestrial DOC substrates was revealed via carbon isotope analysis and mixing models. Thereby, priming was more pronounced for the peat water than for the soil leachate. This indicates that the DOC source and the amount of the added labile organic matter might influence the magnitude of a priming effect. Additional analysis via high-resolution mass spectrometry revealed that oxidized, unsaturated compounds were more strongly decomposed under priming (i.e. in phytoplankton presence). Given the observed increase in DOC concentrations during the experiments, it can be concluded that aquatic priming is not easily detectable via net concentration changes alone and could be considered as a qualitative effect.
The knowledge gained from this thesis contributes to the understanding of aquatic carbon cycling and demonstrated how DOC dynamics in freshwaters vary with hydrological, seasonal and trophic conditions. It further demonstrated that aquatic priming contributes to the microbial transformation of organic carbon and the observed decay of allochthonous DOC during transport in inland waters.
For several decades, researchers have tried to explain how speakers of more than one language (multilinguals) manage to keep their languages separate and to switch from one language to the other depending on the context. This ability of multilingual speakers to use the intended language, while avoiding interference from the other language(s) has recently been termed “language control”.
A multitude of studies showed that when bilinguals process one language, the other language is also activated and might compete for selection. According to the most influential model of language control developed over the last two decades, competition from the non-intended language is solved via inhibition. In particular, the Inhibitory Control (IC) model proposed by Green (1998) puts forward that the amount of inhibition applied to the non-relevant language depends on its dominance, in that the stronger the language the greater the strength of inhibition applied to it. Within this account, the cost required to reactivate a previously inhibited language depends on the amount of inhibition previously exerted on it, that is, reactivation costs are greater for a stronger compared to a weaker language. In a nutshell, according to the IC model, language control is determined by language dominance.
The goal of the present dissertation is to investigate the extent to which language control in multilinguals is affected by language dominance and whether and how other factors might influence this process. Three main factors are considered in this work: (i) the time speakers have to prepare for a certain language or PREPARATION TIME, (ii) the type of languages involved in the interactional context or LANGUAGE TYPOLOGY, and (iii) the PROCESSING MODALITY, that is, whether the way languages are controlled differs between reception and production.
The results obtained in the four manuscripts, either published or in revision, indicate that language dominance alone does not suffice to explain language switching patterns. In particular, the present thesis shows that language control is profoundly affected by each of the three variables described above. More generally, the findings obtained in the present dissertation indicate that language control in multilingual speakers is a much more dynamic system than previously believed and is not exclusively determined by language dominance, as predicted by the IC model (Green, 1998).
The timing and location of the two largest earthquakes of the 21st century (Sumatra, 2004 and Tohoku 2011, events) greatly surprised the scientific community, indicating that the deformation processes that precede and follow great megathrust earthquakes remain enigmatic. During these phases before and after the earthquake a combination of multi-scale complex processes are acting simultaneously: Stresses built up by long-term tectonic motions are modified by sudden jerky deformations during earthquakes, before being restored by multiple ensuing relaxation processes.
This thesis details a cross-scale thermomechanical model developed with the aim of simulating the entire subduction process from earthquake (1 minute) to million years’ time scale, excluding only rupture propagation. The model employs elasticity, non-linear transient viscous rheology, and rate-and-state friction. It generates spontaneous earthquake sequences, and, by using an adaptive time-step algorithm, recreates the deformation process as observed naturally over single and multiple seismic cycles. The model is thoroughly tested by comparing results to those from known high- resolution solutions of generic modeling setups widely used in modeling of rupture propagation. It is demonstrated, that while not modeling rupture propagation explicitly, the modeling procedure correctly recognizes the appearance of instability (earthquake) and correctly simulates the cumulative slip at a fault during great earthquake by means of a quasi-dynamic approximation.
A set of 2D models is used to study the effects of non-linear transient rheology on the postseismic processes following great earthquakes. Our models predict that the viscosity in the mantle wedge drops by 3 to 4 orders of magnitude during a great earthquake with magnitude above 9. This drop in viscosity results in spatial scales and timings of the relaxation processes following the earthquakes that are significantly different to previous estimates. These models replicate centuries long seismic cycles exhibited by the greatest earthquakes (like the Great Chile 1960 Earthquake) and are consistent with the major features of postseismic surface displacements recorded after the Great Tohoku Earthquake.
The 2D models are also applied to study key factors controlling maximum magnitudes of earthquakes in subduction zones. Even though methods of instrumentally observing earthquakes at subduction zones have rapidly improved in recent decades, the characteristic recurrence interval of giant earthquakes (Mw>8.5) is much larger than the currently available observational record and therefore the necessary conditions for giant earthquakes are not clear. Statistical studies have recognized the importance of the slab shape and its surface roughness, state of the strain of the upper plate and thickness of sediments filling the trenches. In this thesis we attempt to explain these observations and to identify key controlling parameters. We test a set of 2D models representing great earthquake seismic cycles at known subduction zones with various known geometries, megathrust friction coefficients, and convergence rates implemented. We found that low-angle subduction (large effect) and thick sediments in the subduction channel (smaller effect) are the fundamental necessary conditions for generating giant earthquakes, while the change of subduction velocity from 10 to 3.5 cm/yr has a lower effect. Modeling results also suggest that having thick sediments in the subduction channel causes low static friction, resulting in neutral or slightly compressive deformation in the overriding plate for low-angle subduction zones. These modeling results agree well with observations for the largest earthquakes. The model predicts the largest possible earthquakes for subduction zones of given dipping angles. The predicted maximum magnitudes exactly threshold magnitudes of all known giant earthquakes of 20th and 21st centuries.
The clear limitation of most of the models developed in the thesis is their 2D nature. Development of 3D models with comparable resolution and complexity will require significant advances in numerical techniques. Nevertheless, we conducted a series of low-resolution 3D models to study the interaction between two large asperities at a subduction interface separated by an aseismic gap of varying width. The novelty of the model is that it considers behavior of the asperities during multiple seismic cycles. As expected, models show that an aseismic gap with a narrow width could not prevent rupture propagation from one asperity to another, and that rupture always crosses the entire model. When the gap becomes too wide, asperities do not interact anymore and rupture independently. However, an interesting mode of interaction was observed in the model with an intermediate width of the aseismic gap: In this model the asperities began to stably rupture in anti-phase following multiple seismic cycles. These 3D modeling results, while insightful, must be considered preliminary because of the limitations in resolution.
The technique developed in this thesis for cross-scale modeling of seismic cycles can be used to study the effects of multiple seismic cycles on the long-term deformation of the upper plate. The technique can be also extended to the case of continental transform faults and for the advanced 3D modeling of specific subduction zones. This will require further development of numerical techniques and adaptation of the existing advanced highly scalable parallel codes like LAMEM and ASPECT.
The functioning of the surface water-groundwater interface as buffer, filter and reactive zone is important for water quality, ecological health and resilience of streams and riparian ecosystems. Solute and heat exchange across this interface is driven by the advection of water. Characterizing the flow conditions in the streambed is challenging as flow patterns are often complex and multidimensional, driven by surface hydraulic gradients and groundwater discharge. This thesis presents the results of an integrated approach of studies, ranging from the acquisition of field data, the development of analytical and numerical approaches to analyse vertical temperature profiles to the detailed, fully-integrated 3D numerical modelling of water and heat flux at the reach scale. All techniques were applied in order to characterize exchange flux between stream and groundwater, hyporheic flow paths and temperature patterns.
The study was conducted at a reach-scale section of the lowland Selke River, characterized by distinctive pool riffle sequences and fluvial islands and gravel bars. Continuous time series of hydraulic heads and temperatures were measured at different depths in the river bank, the hyporheic zone and within the river. The analyses of the measured diurnal temperature variation in riverbed sediments provided detailed information about the exchange flux between river and groundwater. Beyond the one-dimensional vertical water flow in the riverbed sediment, hyporheic and parafluvial flow patterns were identified. Subsurface flow direction and magnitude around fluvial islands and gravel bars at the study site strongly depended on the position around the geomorphological structures and on the river stage. Horizontal water flux in the streambed substantially impacted temperature patterns in the streambed. At locations with substantial horizontal fluxes the penetration depths of daily temperature fluctuations was reduced in comparison to purely vertical exchange conditions.
The calibrated and validated 3D fully-integrated model of reach-scale water and heat fluxes across the river-groundwater interface was able to accurately represent the real system. The magnitude and variations of the simulated temperatures matched the observed ones, with an average mean absolute error of 0.7 °C and an average Nash Sutcliffe Efficiency of 0.87. The simulation results showed that the water and heat exchange at the surface water-groundwater interface is highly variable in space and time with zones of daily temperature oscillations penetrating deep into the sediment and spots of daily constant temperature following the average groundwater temperature. The average hyporheic flow path temperature was found to strongly correlate with the flow path residence time (flow path length) and the temperature gradient between river and groundwater. Despite the complexity of these processes, the simulation results allowed the derivation of a general empirical relationship between the hyporheic residence times and temperature patterns. The presented results improve our understanding of the complex spatial and temporal dynamics of water flux and thermal processes within the shallow streambed. Understanding these links provides a general basis from which to assess hyporheic temperature conditions in river reaches.
Trends in precipitation over Germany and the Rhine basin related to changes in weather patterns
(2017)
Precipitation as the central meteorological feature for agriculture, water security, and human well-being amongst others, has gained special attention ever since. Lack of precipitation may have devastating effects such as crop failure and water scarcity. Abundance of precipitation, on the other hand, may as well result in hazardous events such as flooding and again crop failure. Thus, great effort has been spent on tracking changes in precipitation and relating them to underlying processes. Particularly in the face of global warming and given the link between temperature and atmospheric water holding capacity, research is needed to understand the effect of climate change on precipitation.
The present work aims at understanding past changes in precipitation and other meteorological variables. Trends were detected for various time periods and related to associated changes in large-scale atmospheric circulation. The results derived in this thesis may be used as the foundation for attributing changes in floods to climate change. Assumptions needed for the downscaling of large-scale circulation model output to local climate stations are tested and verified here.
In a first step, changes in precipitation over Germany were detected, focussing not only on precipitation totals, but also on properties of the statistical distribution, transition probabilities as a measure for wet/dry spells, and extreme precipitation events.
Shifting the spatial focus to the Rhine catchment as one of the major water lifelines of Europe and the largest river basin in Germany, detected trends in precipitation and other meteorological variables were analysed in relation to states of an ``optimal'' weather pattern classification. The weather pattern classification was developed seeking the best skill in explaining the variance of local climate variables.
The last question addressed whether observed changes in local climate variables are attributable to changes in the frequency of weather patterns or rather to changes within the patterns itself. A common assumption for a downscaling approach using weather patterns and a stochastic weather generator is that climate change is expressed only as a changed occurrence of patterns with the pattern properties remaining constant. This assumption was validated and the ability of the latest generation of general circulation models to reproduce the weather patterns was evaluated.
% Paper 1
Precipitation changes in Germany in the period 1951-2006 can be summarised briefly as negative in summer and positive in all other seasons. Different precipitation characteristics confirm the trends in total precipitation: while winter mean and extreme precipitation have increased, wet spells tend to be longer as well (expressed as increased probability for a wet day followed by another wet day). For summer the opposite was observed: reduced total precipitation, supported by decreasing mean and extreme precipitation and reflected in an increasing length of dry spells.
Apart from this general summary for the whole of Germany, the spatial distribution within the country is much more differentiated. Increases in winter precipitation are most pronounced in the north-west and south-east of Germany, while precipitation increases are highest in the west for spring and in the south for autumn. Decreasing summer precipitation was observed in most regions of Germany, with particular focus on the south and west.
The seasonal picture, however, was again differently represented in the contributing months, e.g.\ increasing autumn precipitation in the south of Germany is formed by strong trends in the south-west in October and in the south-east in November. These results emphasise the high spatial and temporal organisation of precipitation changes.
% Paper 2
The next step towards attributing precipitation trends to changes in large-scale atmospheric patterns was the derivation of a weather pattern classification that sufficiently stratifies the local climate variables under investigation. Focussing on temperature, radiation, and humidity in addition to precipitation, a classification based on mean sea level pressure, near-surface temperature, and specific humidity was found to have the best skill in explaining the variance of the local variables. A rather high number of 40 patterns was selected, allowing typical pressure patterns being assigned to specific seasons by the associated temperature patterns. While the skill in explaining precipitation variance is rather low, better skill was achieved for radiation and, of course, temperature.
Most of the recent GCMs from the CMIP5 ensemble were found to reproduce these weather patterns sufficiently well in terms of frequency, seasonality, and persistence.
% Paper 3
Finally, the weather patterns were analysed for trends in pattern frequency, seasonality, persistence, and trends in pattern-specific precipitation and temperature. To overcome uncertainties in trend detection resulting from the selected time period, all possible periods in 1901-2010 with a minimum length of 31 years were considered. Thus, the assumption of a constant link between patterns and local weather was tested rigorously. This assumption was found to hold true only partly. While changes in temperature are mainly attributable to changes in pattern frequency, for precipitation a substantial amount of change was detected within individual patterns.
Magnitude and even sign of trends depend highly on the selected time period. The frequency of certain patterns is related to the long-term variability of large-scale circulation modes.
Changes in precipitation were found to be heterogeneous not only in space, but also in time - statements on trends are only valid for the specific time period under investigation. While some part of the trends can be attributed to changes in the large-scale circulation, distinct changes were found within single weather patterns as well.
The results emphasise the need to analyse multiple periods for thorough trend detection wherever possible and add some note of caution to the application of downscaling approaches based on weather patterns, as they might misinterpret the effect of climate change due to neglecting within-type trends.
This study was inspired by the desire to contribute to literature on performance management from the context of a developing country. The guiding research questions were: How do managers use performance information in decision making? Why do managers use performance information the way they do? The study was based on theoretical strands of neo-patrimonialism and new institutionalism. The nature of the inquiry informed the choice of a qualitative case study research design. Data was assembled through face-to-face interviews, some observations, and collection of documents from managers at the levels of the directorate, division, and section/units. The managers who were the focus of this study are current or former staff members of the state departments in Kenya’s national Ministry of Agriculture, Livestock, and Fisheries as well as from departments responsible for coordination of performance related reforms.
The findings of this study show that performance information is regularly produced but its use by managers varies. Examples of use include preparing reports to external bodies, making decisions for resource re-allocation, making recommendations for rewards and sanctions, and policy advisory. On categorizing the forms of use as passive, purposeful, political or perverse, evidence shows that they overlap and that some of the forms are so closely related that it is difficult to separate them empirically.
On what can explain the forms of use established, four factors namely; political will and leadership; organizational capacity; administrative culture; and managers’ interests and attitudes, were investigated. While acknowledging the interrelatedness and even overlapping of the factors, the study demonstrates that there is explanatory power to each though with varying depth and scope. The study thus concludes that: Inconsistent political will and leadership for performance management reforms explain forms of use that are passive, political and perverse. Low organizational capacity could best explain passive and some limited aspects of purposeful use. Informal, personal and competitive administrative culture is associated with purposeful use and mostly with political and perverse use. Limited interest and apprehensive attitude are best associated with passive use.
The study contributes to the literature particularly in how institutions in a context of neo-patrimonialism shape performance information use. It recommends that further research is necessary to establish how neo-patrimonialism positively affects performance oriented reforms. This is interesting in particular given the emerging thinking on pockets of effectiveness and developmental patrimonialism. This is important since it is expected that performance related reforms will continue to be advocated in developing countries in the foreseeable future.
Thermal cis-trans isomerization of azobenzene studied by path sampling and QM/MM stochastic dynamics
(2017)
Azobenzene-based molecular photoswitches have extensively been applied to biological systems, involving photo-control of peptides, lipids and nucleic acids. The isomerization between the stable trans and the metastable cis state of the azo moieties leads to pronounced changes in shape and other physico-chemical properties of the molecules into which they are incorporated. Fast switching can be induced via transitions to excited electronic states and fine-tuned by a large number of different substituents at the phenyl rings. But a rational design of tailor-made azo groups also requires control of their stability in the dark, the half-lifetime of the cis isomer. In computational chemistry, thermally activated barrier crossing on the ground state Born-Oppenheimer surface can efficiently be estimated with Eyring’s transition state theory (TST) approach; the growing complexity of the azo moiety and a rather heterogeneous environment, however, may render some of the underlying simplifying assumptions problematic.
In this dissertation, a computational approach is established to remove two restrictions at once: the environment is modeled explicitly by employing a quantum mechanical/molecular mechanics (QM/MM) description; and the isomerization process is tracked by analyzing complete dynamical pathways between stable states. The suitability of this description is validated by using two test systems, pure azo benzene and a derivative with electron donating and electron withdrawing substituents (“push-pull” azobenzene). Each system is studied in the gas phase, in toluene and in polar DMSO solvent. The azo molecules are treated at the QM level using a very recent, semi-empirical approximation to density functional theory (density functional tight binding approximation). Reactive pathways are sampled by implementing a version of the so-called transition path sampling method (TPS), without introducing any bias into the system dynamics. By analyzing ensembles of reactive trajectories, the change in isomerization pathway from linear inversion to rotation in going from apolar to polar solvent, predicted by the TST approach, could be verified for the push-pull derivative. At the same time, the mere presence of explicit solvation is seen to broaden the distribution of isomerization pathways, an effect TST cannot account for.
Using likelihood maximization based on the TPS shooting history, an improved reaction coordinate was identified as a sine-cosine combination of the central bend angles and the rotation dihedral, r (ω,α,α′). The computational van’t Hoff analysis for the activation entropies was performed to gain further insight into the differential role of solvent for the case of the unsubstituted and the push-pull azobenzene. In agreement with the experiment, it yielded positive activation entropies for azobenzene in the DMSO solvent while negative for the push-pull derivative, reflecting the induced ordering of solvent around the more dipolar transition state associated to the latter compound. Also, the dynamically corrected rate constants were evaluated using the reactive flux approach where an increase comparable to the experimental one was observed for a high polarity medium for both azobenzene derivatives.
We analyze an inverse noisy regression model under random design with the aim of estimating the unknown target function based on a given set of data, drawn according to some unknown probability distribution. Our estimators are all constructed by kernel methods, which depend on a Reproducing Kernel Hilbert Space structure using spectral regularization methods.
A first main result establishes upper and lower bounds for the rate of convergence under a given source condition assumption, restricting the class of admissible distributions. But since kernel methods scale poorly when massive datasets are involved, we study one example for saving computation time and memory requirements in more detail. We show that Parallelizing spectral algorithms also leads to minimax optimal rates of convergence provided the number of machines is chosen appropriately.
We emphasize that so far all estimators depend on the assumed a-priori smoothness of the target function and on the eigenvalue decay of the kernel covariance operator, which are in general unknown. To obtain good purely data driven estimators constitutes the problem of adaptivity which we handle for the single machine problem via a version of the Lepskii principle.
Culture-driven innovation
(2017)
This cumulative dissertation deals with the potential of underexplored cultural sources for innovation.
Nowadays, firms recognize an increasing demand for innovation to keep pace with an ever-growing dynamic worldwide competition. Knowledge is one of the most crucial sources and resource, while until now innovation has been foremost driven by technology. But since the last years, we have been witnessing a change from technology's role as a driver of innovation to an enabler of innovation. Innovative products and services increasingly differentiate through emotional qualities and user experience. These experiences are hard to grasp and require alignment in innovation management theory and practice.
This work cares about culture in a broader matter as a source for innovation. It investigates the requirements and fundamentals for "culture-driven innovation" by studying where and how to unlock cultural sources. The research questions are the following: What are cultural sources for knowledge and innovation? Where can one find cultural sources and how to tap into them?
The dissertation starts with an overview of its central terms and introduces cultural theories as an overarching frame to study cultural sources for innovation systematically. Here, knowledge is not understood as something an organization owns like a material resource, but it is seen as something created and taking place in practices. Such a practice theoretical lens inheres the rejection of the traditional economic depiction of the rational Homo Oeconomicus. Nevertheless, it also rejects the idea of the Homo Sociologicus about the strong impact of society and its values on individual actions. Practice theory approaches take account of both concepts by underscoring the dualism of individual (agency, micro-level) and structure (society, macro-level). Following this, organizations are no enclosed entities but embedded within their socio-cultural environment, which shapes them and is also shaped by them.
Then, the first article of this dissertation acknowledges a methodological stance of this dualism by discussing how mixed methods support an integrated approach to study the micro- and macro-level. The article focuses on networks (thus communities) as a central research unit within studies of entrepreneurship and innovation.
The second article contains a network analysis and depicts communities as central loci for cultural sources and knowledge. With data from the platform Meetup.com about events etc., the study explores which overarching communities and themes have been evolved in Berlin's start up and tech scene.
While the latter study was about where to find new cultural sources, the last article addresses how to unlock such knowledge sources. It develops the concept of a cultural absorptive capacity, that is the capability of organizations to open up towards cultural sources. Furthermore, the article points to the role of knowledge intermediaries in the early phases of knowledge acquisition. Two case studies on companies working with artists illustrate the roles of such intermediaries and how they support firms to gain knowledge from cultural sources.
Overall, this dissertation contributes to a better understanding of culture as a source for innovation from a theoretical, methodological, and practitioners' point of view. It provides basic research to unlock the potential of such new knowledge sources for companies - sources that so far have been neglected in innovation management.
Bobrowski hatte nach dem Abitur die Absicht geäußert, Kunstgeschichte zu studieren, doch Krieg und Kriegsgefangenschaft vereitelten seinen Plan: Der Wehrmachtsangehörige wurde einzig im Winter 1941/1942 für ein Studiensemester an der Universität Berlin vom Kriegsdienst freigestellt. Nachhaltig beeindruckt war Bobrowski insbesondere von der Vorlesung „Deutsche Kunst der Goethezeit“ des Lehrstuhlinhabers Wilhelm Pinder. Trotz eines grundlegenden Einflusses ist indessen zu keinem Zeitpunkt Pinders ideologischer Hintergrund in Bobrowskis Gedichten manifest geworden. Nach der Rückkehr aus sowjetischer Gefangenschaft an Weihnachten 1949 war für den mittlerweile Zweiunddreißigjährigen an ein Studium nicht mehr zu denken. Die lebenslange intermediale Auseinandersetzung mit Werken der bildenden Kunst in seinem Œuvre kann indessen als Ausdruck seiner vielfältigen kulturgeschichtlichen Interessen und Neigungen interpretiert werden. Die Lebensphasen des Dichters korrelieren mit einer motivischen Entwicklung seiner Bildgedichte: Insbesondere half ihm die unantastbare Ästhetik bedeutender Kunstwerke, das Grauen der letzten Kriegsjahre und die Entbehrungen in sowjetischer Kriegsgefangenschaft zu überwinden. Didaktisch-moralische Zielsetzungen prägten zunächst die in den Jahren nach seiner Heimkehr entstandenen Gedichte, bevor sich Bobrowski inhaltlich und formal von diesem Gedichttypus zu lösen vermochte und vermehrt Gedichte zu schreiben begann, die kulturgeschichtliche Dimensionen annahmen und historische, mythologische, biblische und religionsphilosophische Themen in epochenübergreifende Zusammenhänge stellten. Die Gedichte über die Künstler Jawlensky und Calder berühren gleichzeitig kulturlandschaftliche Aspekte. Im letzten Lebensjahrzehnt interessierte sich Bobrowski zunehmend für die Kunst des 20. Jahrhunderts, während die moderne Architektur aus seinem Werk ausgeklammert blieb.
Architektur bildet eine Leitmotivik in Bobrowskis lyrischem Werk. Die übertragene Bedeutungsebene der in den Gedichten benannten sakralen und profanen Einzelbauten, aber auch der städtischen und dörflichen Ensembles sowie einzelner Gebäudeteile, verändert sich mehrfach im Laufe der Jahre. Ausgehend von traditionellen, paargereimten Jugendgedichten in jambischem Versmaß, in denen architektonische Elemente Teil einer Wahrnehmung bilden, die alles Außerästhetische ausblendet, wandelt sich der Sinngehalt der Sakral- und Profanbauten in Bobrowskis lyrischem Werk ein erstes Mal während den Kriegsjahren in Russland, die der Wehrmachtsangehörige am Ilmensee verbracht hat. In den damals entstandenen Oden zeugen die architektonischen Relikte von Leid, Tod und Zerstörung. Noch fehlt indessen der später so zentrale Gedanke der Schuld, der erst im Rückblick auf jene Zeit in den Gedichten, die nach der Rückkehr aus der Kriegsgefangenschaft bis zu Bobrowskis frühem Tod entstanden sind, thematisiert worden ist.
Gegen Ende des Kriegs und in den Jahren der Kriegsgefangenschaft besinnt sich Bobrowski erneut auf Heimatthemen, und die Architektur in seinen Gedichten wird zu einem ästhetisch überhöhten Fluchtpunkt seiner Sehnsucht nach Ostpreußen und dem Memelgebiet. In Kriegsgefangenschaft tritt erstmals der Aspekt des Sublimen in seinen Gedichten auf, und zwar sowohl bezogen auf die Malerei als auch auf die Architektur. Dieser Gedanke wird einerseits nach der Rückkehr nach Berlin in den Gedichten über die Architektur gotischer Kathedralen und das bauliche Erbe des Klassizismus weitergesponnen, doch steht in den damals entstandenen Gedichten das Kulturerbe Europas auch für historisches Unrecht und eine schwere, weit zurückreichende Schuld.
Von dieser auf den ganzen Kontinent bezogenen Kritik wendet sich Bobrowski in den nachfolgenden Jahren ab und konzentriert sich auf die Schuld der Deutschen gegenüber den Völkern Osteuropas. Damit erhält auch die Architektur in seinen Gedichten eine neue Bedeutung. Die Relikte der Ritterburgen des deutschen Ordens zeugen von der Herrschaft der mittelalterlichen Eroberer und verschmelzen dabei mit der Natur: Das Zeichenhafte der Architektur wird Teil der Landschaft. Im letzten Lebensjahrzehnt entstehen vermehrt Gedichte, die sich auf Parkanlagen und städtische Grünräume beziehen.
Der Dichter hat sich nicht nur auf persönliche Erfahrungen, sondern mitunter auch auf Bildquellen abstützt, ohne dass er das Original je gesehen hätte. Nur schwer zugänglich sind die Gedichte über Chagall und Gauguin ohne die Erkenntnis, dass sie sich auf Bildvorlagen in schmalen, populärwissenschaftlichen Büchern beziehen, die Bobrowski jeweils kurz vor der Niederschrift der entsprechenden Gedichte erworben hat. Anders verhält es sich mit jenen russischen Kirchen, die Eingang in sein lyrisches Werk gefunden haben. Bobrowski hat sie alle selbst im Krieg gesehen, und die meisten scheinen noch heute zu bestehen und können mit einiger Sicherheit identifiziert werden, wozu auch die Briefe des Dichters aus jener Zeit beitragen.
Trunk loading and back pain
(2017)
An essential function of the trunk is the compensation of external forces and loads in order to guarantee stability. Stabilising the trunk during sudden, repetitive loading in everyday tasks, as well as during performance is important in order to protect against injury. Hence, reduced trunk stability is accepted as a risk factor for the development of back pain (BP). An altered activity pattern including extended response and activation times as well as increased co-contraction of the trunk muscles as well as a reduced range of motion and increased movement variability of the trunk are evident in back pain patients (BPP). These differences to healthy controls (H) have been evaluated primarily in quasi-static test situations involving isolated loading directly to the trunk. Nevertheless, transferability to everyday, dynamic situations is under debate. Therefore, the aim of this project is to analyse 3-dimensional motion and neuromuscular reflex activity of the trunk as response to dynamic trunk loading in healthy (H) and back pain patients (BPP).
A measurement tool was developed to assess trunk stability, consisting of dynamic test situations. During these tests, loading of the trunk is generated by the upper and lower limbs with and without additional perturbation. Therefore, lifting of objects and stumbling while walking are adequate represents. With the help of a 12-lead EMG, neuromuscular activity of the muscles encompassing the trunk was assessed. In addition, three-dimensional trunk motion was analysed using a newly developed multi-segmental trunk model. The set-up was checked for reproducibility as well as validity. Afterwards, the defined measurement set-up was applied to assess trunk stability in comparisons of healthy and back pain patients.
Clinically acceptable to excellent reliability could be shown for the methods (EMG/kinematics) used in the test situations. No changes in trunk motion pattern could be observed in healthy adults during continuous loading (lifting of objects) of different weights. In contrast, sudden loading of the trunk through perturbations to the lower limbs during walking led to an increased neuromuscular activity and ROM of the trunk. Moreover, BPP showed a delayed muscle response time and extended duration until maximum neuromuscular activity in response to sudden walking perturbations compared to healthy controls. In addition, a reduced lateral flexion of the trunk during perturbation could be shown in BPP.
It is concluded that perturbed gait seems suitable to provoke higher demands on trunk stability in adults. The altered neuromuscular and kinematic compensation pattern in back pain patients (BPP) can be interpreted as increased spine loading and reduced trunk stability in patients. Therefore, this novel assessment of trunk stability is suitable to identify deficits in BPP. Assignment of affected BPP to therapy interventions with focus on stabilisation of the trunk aiming to improve neuromuscular control in dynamic situations is implied. Hence, sensorimotor training (SMT) to enhance trunk stability and compensation of unexpected sudden loading should be preferred.
Im Sinne des Refinements von Tierversuchen sollen alle Bedingungen während der Zucht, der Haltung und des Transports von zu Versuchszwecken gehaltenen Tieren und alle Methoden während des Versuchs so verbessert werden, dass die verwendeten Tiere ein minimales Maß an potentiellem Distress, Schmerzen oder Leiden erfahren. Zudem soll ihr Wohlbefinden durch die Möglichkeit des Auslebens speziesspezifischer Verhaltensweisen und die Anwendung tierschonender Verfahren maximal gefördert werden. Zur Etablierung von Grundsätzen des Refinements sind grundlegende Kenntnisse über die physiologischen Bedürfnisse und Verhaltensansprüche der jeweiligen Spezies unabdingbar. Die Experimentatoren sollten das Normalverhalten der Tiere kennen, um potentielle Verhaltensabweichungen, wie Stereotypien, zu verstehen und interpretieren zu können. Standardisierte Haltungsbedingungen von zu Versuchszwecken gehaltenen Mäusen weichen in diversen Aspekten von der natürlichen Umgebung ab und erfordern eine gewisse Adaptation. Ist ein Tier über einen längeren Zeitraum unfähig, sich an die gegebenen Umstände anzupassen, können abnormale Verhaltensweisen, wie Stereotypien auftreten. Stereotypien werden definiert als Abweichungen vom Normalverhalten, die repetitiv und ohne Abweichungen im Ablauf ausgeführt werden, scheinbar keiner Funktion dienen und der konkreten Umweltsituation nicht immer entsprechen.
Bisher war unklar, in welchem Ausmaß stereotypes Verhalten den metabolischen Phänotyp eines Individuums beeinflusst. Ziel dieser Arbeit war es daher, das stereotype Verhalten der FVB/NJ-Maus erstmals detailliert zu charakterisieren, systematisch zusammenzutragen, welche metabolischen Konsequenzen dieses Verhalten bedingt und wie sich diese auf das Wohlbefinden der Tiere und die Verwendung stereotyper Tiere in Studien mit tierexperimentellem Schwerpunkt auswirken.
Der Versuch begann mit der Charakterisierung der mütterlichen Fürsorge in der Parentalgeneration. Insgesamt wurden 35 Jungtiere der F1-Generation vom Absatz an, über einen Zeitraum von 11 Wochen einzeln gehalten, kontinuierlich beobachtet, bis zum Versuchsende wöchentlich Kotproben gesammelt und das Körpergewicht bestimmt. Zusätzlich erfolgten begleitende Untersuchungen wie Verhaltenstests und die Erfassung der physischen Aktivität und metabolischer Parameter. Anschließend wurden u.a. die zerebralen Serotonin- und Dopamingehalte, fäkale Glucocorticoidlevels, hepatisches Glykogen und muskuläre Glykogen- und Triglyceridlevels bestimmt.
Nahezu unabhängig von der mütterlichen Herkunft entwickelte sich bei mehr als der Hälfte der 35 Jungtiere in der F1-Generation stereotypes Verhalten. Diese Daten deuten darauf hin, dass es keine Anzeichen für das Erlernen oder eine direkte genetische Transmission stereotypen Verhaltens bei der FVB/NJ-Maus gibt. Über den gesamten Beobachtungszeitraum zeichneten sich die stereotypen FVB/NJ-Mäuse durch ein eingeschränktes Verhaltensrepertoire aus. Zu Gunsten der erhöhten Aktivität und des Ausübens stereotypen Verhaltens lebten sie insgesamt weniger andere Verhaltensweisen (Klettern, Graben, Nagen) aus. Darüber hinaus waren Stereotypien sowohl im 24-Stunden Open Field Test als auch in der Messeinrichtung der indirekten Tierkalorimetrie mit einer erhöhten Aktivität und Motilität assoziiert, während die circadiane Rhythmik nicht divergierte. Diese erhöhte körperliche Betätigung spiegelte sich in den niedrigeren Körpergewichtsentwicklungen der stereotypen Tiere wieder. Außerdem unterschieden sich die Körperfett- und Körpermuskelanteile.
Zusammenfassend lässt sich sagen, dass das Ausüben stereotypen Verhaltens zu Differenzen im metabolischen Phänotyp nicht-stereotyper und stereotyper FVB/NJ-Mäuse führt. Im Sinne der „Guten Wissenschaftlichen Praxis“ sollte das zentrale Ziel jedes Wissenschaftlers sein, aussagekräftige und reproduzierbare Daten hervorzubringen. Jedoch können keine validen Resultate von Tieren erzeugt werden, die in Aspekten variieren, die für den vorgesehenen Zweck der Studie nicht berücksichtigt wurden. Deshalb sollten nicht-stereotype und stereotype Individuen nicht innerhalb einer Versuchsgruppe randomisiert werden. Stereotype Tiere demzufolge von geplanten Studien auszuschließen, würde allerdings dem Gebot des zweiten R’s – der Reduction – widersprechen. Um Refinement zu garantieren, sollte der Fokus auf der maximal erreichbaren Prävention stereotypen Verhaltens liegen. Diverse Studien haben bereits gezeigt, dass die Anreicherung der Haltungsumwelt (environmental enrichment) zu einer Senkung der Prävalenz von Stereotypien bei Mäusen führt, dennoch kommen sie weiterhin vor. Daher sollte environmental enrichment zukünftig weniger ein „Kann“, sondern ein „Muss“ sein – oder vielmehr: der Goldstandard. Zudem würde eine profunde phänotypische Charakterisierung dazu beitragen, Mausstämme zu erkennen, die zu Stereotypien neigen und den für den spezifischen Zweck am besten geeigneten Mausstamm zu identifizieren, bevor ein Experiment geplant wird.
The field of nanophotonics focuses on the interaction between electromagnetic radiation and matter on the nanometer scale. The elements of nanoscale photonic devices can transfer excitation energy non-radiatively from an excited donor molecule to an acceptor molecule by Förster resonance energy transfer (FRET). The efficiency of this energy transfer is highly dependent on the donor-acceptor distance. Hence, in these nanoscale photonic devices it is of high importance to have a good control over the spatial assembly of used fluorophores. Based on molecular self-assembly processes, various nanostructures can be produced. Here, DNA nanotechnology and especially the DNA origami technique are auspicious self-assembling methods. By using DNA origami nanostructures different fluorophores can be introduced with a high local control to create a variety of nanoscale photonic objects. The applications of such nanostructures range from photonic wires and logic gates for molecular computing to artificial light harvesting systems for artificial photosynthesis.
In the present cumulative doctoral thesis, different FRET systems on DNA origami structures have been designed and thoroughly analyzed. Firstly, the formation of guanine (G) quadruplex structures from G rich DNA sequences has been studied based on a two-color FRET system (Fluorescein (FAM)/Cyanine3 (Cy3)). Here, the influences of different cations (Na+ and K+), of the DNA origami structure and of the DNA sequence on the G-quadruplex formation have been analyzed. In this study, an ion-selective K+ sensing scheme based on the G-quadruplex formation on DNA origami structures has been developed. Subsequently, the reversibility of the G-quadruplex formation on DNA origami structures has been evaluated. This has been done for the simple two-color FRET system which has then been advanced to a switchable photonic wire by introducing additional fluorophores (FAM/Cy3/Cyanine5 (Cy5)/IRDye®700). In the last part, the emission intensity of the acceptor molecule (Cy5) in a three-color FRET cascade has been tuned by arranging multiple donor (FAM) and transmitter (Cy3) molecules around the central acceptor molecule. In such artificial light harvesting systems, the excitation energy is absorbed by several donor and transmitter molecules followed by an energy transfer to the acceptor leading to a brighter Cy5 emission. Furthermore, the range of possible excitation wavelengths is extended by using several different fluorophores (FAM/Cy3/Cy5). In this part of the thesis, the light harvesting efficiency (antenna effect) and the FRET efficiency of different donor/transmitter/acceptor assemblies have been analyzed and the artificial light harvesting complex has been optimized in this respect.
Lithospheric plates move over the low viscosity asthenosphere balancing several forces. The driving forces include basal shear stress exerted by mantle convection and plate boundary forces such as slab pull and ridge push, whereas the resisting forces include inter-plate friction, trench resistance, and cratonic root resistance. These generate plate motions, the lithospheric stress field and dynamic topography which are observed with different geophysical methods. The orientation and tectonic regime of the observed crustal/lithospheric stress field further contribute to our knowledge of different deformation processes occurring within the Earth's crust and lithosphere. Using numerical models previous studies were able to identify major forces generating stresses in the crust and lithosphere which also contribute to the formation of topography as well as driving lithospheric plates. They showed that the first-order stress pattern explaining about 80\,\% of the stress field originates from a balance of forces acting at the base of the moving lithospheric plates due to convective flow in the underlying mantle. The remaining second-order stress pattern is due to lateral density variations in the crust and lithosphere in regions of pronounced topography and high gravitational potential, such as the Himalayas and mid-ocean ridges. By linking global lithosphere dynamics to deep mantle flow this study seeks to evaluate the influence of shallow and deep density heterogenities on plate motions, lithospheric stress field and dynamic topography using the geoid as a major constraint for mantle rheology. We use the global 3D lithosphere-asthenosphere model SLIM3D with visco-elasto-plastic rheology coupled at 300 km depth to a spectral model of mantle flow. The complexity of the lithosphere-asthenosphere component allows for the simulation of power-law rheology with creep parameters accounting for both diffusion and dislocation creep within the uppermost 300 km.
First we investigate the influence of intra-plate friction and asthenospheric viscosity on present-day plate motions. Previous modelling studies have suggested that small friction coefficients (µ < 0.1, yield stress ~ 100 MPa) can lead to plate tectonics in models of mantle convection. Here we show that, in order to match present-day plate motions and net rotation, the frictional parameter must be less than 0.05. We are able to obtain a good fit with the magnitude and orientation of observed plate velocities (NUVEL-1A) in a no-net-rotation (NNR) reference frame with µ < 0.04 and minimum asthenosphere viscosity ~ 5*10e19 Pas to 10e20 Pas. Our estimates of net rotation (NR) of the lithosphere suggest that amplitudes ~ 0.1-0.2 °/Ma, similar to most observation-based estimates, can be obtained with asthenosphere viscosity cutoff values of ~ 10e19 Pas to 5*10e19 Pas and friction coefficient µ < 0.05.
The second part of the study investigates further constraints on shallow and deep mantle heterogeneities causing plate motion by predicting lithosphere stress field and topography and validating with observations. Lithosphere stresses and dynamic topography are computed using the modelling setup and rheological parameters for prescribed plate motions. We validate our results with the World Stress Map 2016 (WSM2016) and the observed residual topography. Here we tested a number of upper mantle thermal-density structures. The one used to calculate plate motions is considered the reference thermal-density structure. This model is derived from a heat flow model combined with a sea floor age model. In addition we used three different thermal-density structures derived from global S-wave velocity models to show the influence of lateral density heterogeneities in the upper 300 km on model predictions. A large portion of the total dynamic force generating stresses in the crust/lithosphere has its origin in the deep mantle, while topography is largely influenced by shallow heterogeneities. For example, there is hardly any difference between the stress orientation patterns predicted with and without consideration of the heterogeneities in the upper mantle density structure across North America, Australia, and North Africa. However, the crust is dominant in areas of high altitude for the stress orientation compared to the all deep mantle contribution.
This study explores the sensitivity of all the considered surface observables with regards to model parameters providing insights into the influence of the asthenosphere and plate boundary rheology on plate motion as we test various thermal-density structures to predict stresses and topography.
Underground coal gasification (UCG) has the potential to increase worldwide coal reserves by developing coal resources, currently not economically extractable by conventional mining methods. For that purpose, coal is combusted in situ to produce a high-calorific synthesis gas with different end-use options, including electricity generation as well as production of fuels and chemical feedstock. Apart from the high economic potentials, UCG may induce site‐specific environmental impacts, including ground surface subsidence and pollutant migration of UCG by-products into shallow freshwater aquifers. Sustainable and efficient UCG operation requires a thorough understanding of the coupled thermal, hydraulic and mechanical processes, occurring in the UCG reactor vicinity. The development and infrastructure costs of UCG trials are very high; therefore, numerical simulations of coupled processes in UCG are essential for the assessment of potential environmental impacts. Therefore, the aim of the present study is to assess UCG-induced permeability changes, potential hydraulic short circuit formation and non-isothermal multiphase fluid flow dynamics by means of coupled numerical simulations. Simulation results on permeability changes in the UCG reactor vicinity demonstrate that temperature-dependent thermo-mechanical parameters have to be considered in near-field assessments, only. Hence, far-field simulations do not become inaccurate, but benefit from increased computational efficiency when thermo-mechanical parameters are maintained constant. Simulations on potential hydraulic short circuit formation between single UCG reactors at regional-scale emphasize that geologic faults may induce hydraulic connections, and thus compromise efficient UCG operation. In this context, the steam jacket surrounding high-temperature UCG reactors plays a vital role in avoiding UCG by-products escaping into freshwater aquifers and in minimizing energy consumption by formation fluid evaporation. A steam jacket emerges in the close reactor vicinity due to phase transition of formation water and is a non-isothermal flow phenomenon. Considering this complex multiphase flow behavior, an innovative conceptual modeling approach, validated against field data, enables the quantification and prediction of UCG reactor water balances. The findings of this doctoral thesis provide an important basis for integration of thermo-hydro-mechanical simulations in UCG, required for the assessment and mitigation of its potential environmental impacts as well as optimization of its efficiency.
This dissertation explores whether the processing of ellipsis is affected by changes in the complexity of the antecedent, either due to added linguistic material or to the presence of a temporary ambiguity. Murphy (1985) hypothesized that ellipsis is resolved via a string copying procedure when the antecedent is within the same sentence, and that copying longer strings takes more time. Such an account also implies that the antecedent is copied without its structure, which in turn implies that recomputing its syntax and semantics may be necessary at the ellipsis gap. Alternatively, several accounts predict null effects of antecedent complexity, as well as no reparsing. These either involve a structure copying mechanism that is cost-free and whose finishing time is thus independent of the form of the antecedent (Frazier & Clifton, 2001), treat ellipsis as a pointer into content-addressable memory with direct access (Martin & McElree, 2008, 2009), or assume that one structure is ‘shared’ between antecedent and gap (Frazier & Clifton, 2005).
In a self-paced reading study on German sluicing, temporarily ambiguous garden-path clauses were used as antecedents, but no evidence of reparsing in the form of a slowdown at the ellipsis site was found. Instead, results suggest that antecedents which had been reanalyzed from an initially incorrect structure were easier to retrieve at the gap. This finding that can be explained within the framework of cue-based retrieval parsing (Lewis & Vasishth, 2005), where additional syntactic operations on a structure yield memory reactivation effects.
Two further self-paced reading studies on German bare argument ellipsis and English verb phrase ellipsis investigated if adding linguistic content to the antecedent would increase processing times for the ellipsis, and whether insufficiently demanding comprehension tasks may have been responsible for earlier null results (Frazier & Clifton, 2000; Martin & McElree, 2008). It has also been suggested that increased antecedent complexity should shorten rather than lengthen retrieval times by providing more unique memory features (Hofmeister, 2011). Both experiments failed to yield reliable evidence that antecedent complexity affects ellipsis processing times in either direction, irrespectively of task demands.
Finally, two eye-tracking studies probed more deeply into the proposed reactivation-induced speedup found in the first experiment. The first study used three different kinds of French garden-path sentences as antecedents, with two of them failing to yield evidence for reactivation. Moreover, the third sentence type showed evidence suggesting that having failed to assign a structure to the antecedent leads to a slowdown at the ellipsis site, as well as regressions towards the ambiguous part of the sentence. The second eye-tracking study used the same materials as the initial self-paced reading study on German, with results showing a pattern similar to the one originally observed, with some notable differences.
Overall, the experimental results are compatible with the view that adding linguistic material to the antecedent has no or very little effect on the ease with which ellipsis is resolved, which is consistent with the predictions of cost-free copying, pointer-based approaches and structure sharing. Additionally, effects of the antecedent’s parsing history on ellipsis processing may be due to reactivation, the availability of multiple representations in memory, or complete failure to retrieve a matching target.
Data profiling is the computer science discipline of analyzing a given dataset for its metadata. The types of metadata range from basic statistics, such as tuple counts, column aggregations, and value distributions, to much more complex structures, in particular inclusion dependencies (INDs), unique column combinations (UCCs), and functional dependencies (FDs). If present, these statistics and structures serve to efficiently store, query, change, and understand the data. Most datasets, however, do not provide their metadata explicitly so that data scientists need to profile them.
While basic statistics are relatively easy to calculate, more complex structures present difficult, mostly NP-complete discovery tasks; even with good domain knowledge, it is hardly possible to detect them manually. Therefore, various profiling algorithms have been developed to automate the discovery. None of them, however, can process datasets of typical real-world size, because their resource consumptions and/or execution times exceed effective limits.
In this thesis, we propose novel profiling algorithms that automatically discover the three most popular types of complex metadata, namely INDs, UCCs, and FDs, which all describe different kinds of key dependencies. The task is to extract all valid occurrences from a given relational instance. The three algorithms build upon known techniques from related work and complement them with algorithmic paradigms, such as divide & conquer, hybrid search, progressivity, memory sensitivity, parallelization, and additional pruning to greatly improve upon current limitations. Our experiments show that the proposed algorithms are orders of magnitude faster than related work. They are, in particular, now able to process datasets of real-world, i.e., multiple gigabytes size with reasonable memory and time consumption.
Due to the importance of data profiling in practice, industry has built various profiling tools to support data scientists in their quest for metadata. These tools provide good support for basic statistics and they are also able to validate individual dependencies, but they lack real discovery features even though some fundamental discovery techniques are known for more than 15 years. To close this gap, we developed Metanome, an extensible profiling platform that incorporates not only our own algorithms but also many further algorithms from other researchers. With Metanome, we make our research accessible to all data scientists and IT-professionals that are tasked with data profiling. Besides the actual metadata discovery, the platform also offers support for the ranking and visualization of metadata result sets.
Being able to discover the entire set of syntactically valid metadata naturally introduces the subsequent task of extracting only the semantically meaningful parts. This is challenge, because the complete metadata results are surprisingly large (sometimes larger than the datasets itself) and judging their use case dependent semantic relevance is difficult. To show that the completeness of these metadata sets is extremely valuable for their usage, we finally exemplify the efficient processing and effective assessment of functional dependencies for the use case of schema normalization.
Proteins are molecules that are essential for life and carry out an enormous number of functions in organisms. To this end, they change their conformation and bind to other molecules. However, the interplay between conformational change and binding is not fully understood. In this work, this interplay is investigated with molecular dynamics (MD) simulations of the protein-peptide system Mdm2-PMI and by analysis of data from relaxation experiments.
The central task it to uncover the binding mechanism, which is described by the sequence of (partial) binding events and conformational change events including their probabilities. In the simplest case, the binding mechanism is described by a two-step model: binding followed by conformational change or conformational change followed by binding. In the general case, longer sequences with multiple conformational changes and partial binding events are possible as well as parallel pathways that differ in their sequences of events. The theory of Markov state models (MSMs) provides the theoretical framework in which all these cases can be modeled. For this purpose, MSMs are estimated in this work from MD data, and rate equation models, which are related to MSMs, are inferred from experimental relaxation data.
The MD simulation and Markov modeling of the PMI-Mdm2 system shows that PMI and Mdm2 can bind via multiple pathways. A main result of this work is a dissociation rate on the order of one event per second, which was calculated using Markov modeling and is in agreement with experiment. So far, dissociation rates and transition rates of this magnitude have only been calculated with methods that speed up transitions by acting with time-dependent, external forces on the binding partners. The simulation technique developed in this work, in contrast, allows the estimation of dissociation rates from the combination of free energy calculation and direct MD simulation of the fast binding process. Two new statistical estimators TRAM and TRAMMBAR are developed to estimate a MSM from the joint data of both simulation types.
In addition, a new analysis technique for time-series data from chemical relaxation experiments is developed in this work. It allows to identify one of the above-mentioned two-step mechanisms as the mechanism that underlays the data. The new method is valid for a broader range of concentrations than previous methods and therefore allows to choose the concentrations such that the mechanism can be uniquely identified. It is successfully tested with data for the binding of recoverin to a rhodopsin kinase peptide.
I. Ceric ammonium nitrate (CAN) mediated thiocyanate radical additions to glycals
In this dissertation, a facile entry was developed for the synthesis of 2-thiocarbohydrates and their transformations. Initially, CAN mediated thiocyanation of carbohydrates was carried out to obtain the basic building blocks (2-thiocyanates) for the entire studies. Subsequently, 2-thiocyanates were reduced to the corresponding thiols using appropriate reagents and reaction conditions. The screening of substrates, stereochemical outcome and the reaction mechanism are discussed briefly (Scheme I).
Scheme I. Synthesis of the 2-thiocyanates II and reductions to 2-thiols III & IV.
An interesting mechanism was proposed for the reduction of 2-thiocyanates II to 2-thiols III via formation of a disulfide intermediate. The water soluble free thiols IV were obtained by cleaving the thiocyanate and benzyl groups in a single step. In the subsequent part of studies, the synthetic potential of the 2-thiols was successfully expanded by simple synthetic transformations.
II. Transformations of the 2-thiocarbohydrates
The 2-thiols were utilized for convenient transformations including sulfa-Michael additions, nucleophilic substitutions, oxidation to disulfides and functionalization at the anomeric position. The diverse functionalizations of the carbohydrates at the C-2 position by means of the sulfur linkage are the highlighting feature of these studies. Thus, it creates an opportunity to expand the utility of 2-thiocarbohydrates for biological studies.
Reagents and conditions: a) I2, pyridine, THF, rt, 15 min; b) K2CO3, MeCN, rt, 1 h; c) MeI, K2CO3, DMF, 0 °C, 5 min; d) Ac2O, H2SO4 (1 drop), rt, 10 min; e) CAN, MeCN/H2O, NH4SCN, rt, 1 h; f) NaN3, ZnBr2, iPrOH/H2O, reflux, 15 h; g) NaOH (1 M), TBAI, benzene, rt, 2 h; h) ZnCl2, CHCl3, reflux, 3 h.
Scheme II. Functionalization of 2-thiocarbohydrates.
These transformations have enhanced the synthetic value of 2-thiocarbohydrates for the preparative scale. Worth to mention is the Lewis acid catalyzed replacement of the methoxy group by other nucleophiles and the synthesis of the (2→1) thiodisaccharides, which were obtained with complete β-selectivity. Additionally, for the first time, the carbohydrate linked thiotetrazole was synthesized by a (3 + 2) cycloaddition approach at the C-2 position.
III. Synthesis of thiodisaccharides by thiol-ene coupling.
In the final part of studies, the synthesis of thiodisaccharides by a classical photoinduced thiol-ene coupling was successfully achieved.
Reagents and conditions: 2,2-Dimethoxy-2-phenylacetophenone (DPAP), CH2Cl2/EtOH, hv, rt.
Scheme III. Thiol-ene coupling between 2-thiols and exo-glycals.
During the course of investigations, it was found that the steric hindrance plays an important role in the addition of bulky thiols to endo-glycals. Thus, we successfully screened the suitable substrates for addition of various thiols to sterically less hindered alkenes (Scheme III). The photochemical addition of 2-thiols to three different exo-glycals delivered excellent regio- and diastereoselectivities as well as yields, which underlines the synthetic potential of this convenient methodology.
The aim of this thesis is to develop approaches to automatically recognise the structure of argumentation in short monological texts. This amounts to identifying the central claim of the text, supporting premises, possible objections, and counter-objections to these objections, and connecting them correspondingly to a structure that adequately describes the argumentation presented in the text.
The first step towards such an automatic analysis of the structure of argumentation is to know how to represent it. We systematically review the literature on theories of discourse, as well as on theories of the structure of argumentation against a set of requirements and desiderata, and identify the theory of J. B. Freeman (1991, 2011) as a suitable candidate to represent argumentation structure. Based on this, a scheme is derived that is able to represent complex argumentative structures and can cope with various segmentation issues typically occurring in authentic text.
In order to empirically test our scheme for reliability of annotation, we conduct several annotation experiments, the most important of which assesses the agreement in reconstructing argumentation structure. The results show that expert annotators produce very reliable annotations, while the results of non-expert annotators highly depend on their training in and commitment to the task.
We then introduce the 'microtext' corpus, a collection of short argumentative texts. We report on the creation, translation, and annotation of it and provide a variety of statistics. It is the first parallel corpus (with a German and English version) annotated with argumentation structure, and -- thanks to the work of our colleagues -- also the first annotated according to multiple theories of (global) discourse structure.
The corpus is then used to develop and evaluate approaches to automatically predict argumentation structures in a series of six studies: The first two of them focus on learning local models for different aspects of argumentation structure. In the third study, we develop the main approach proposed in this thesis for predicting globally optimal argumentation structures: the 'evidence graph' model. This model is then systematically compared to other approaches in the fourth study, and achieves state-of-the-art results on the microtext corpus. The remaining two studies aim to demonstrate the versatility and elegance of the proposed approach by predicting argumentation structures of different granularity from text, and finally by using it to translate rhetorical structure representations into argumentation structures.
In this thesis, stochastic dynamics modelling collective motions of populations, one of the most mysterious type of biological phenomena, are considered. For a system of N particle-like individuals, two kinds of asymptotic behaviours are studied : ergodicity and flocking properties, in long time, and propagation of chaos, when the number N of agents goes to infinity. Cucker and Smale, deterministic, mean-field kinetic model for a population without a hierarchical structure is the starting point of our journey : the first two chapters are dedicated to the understanding of various stochastic dynamics it inspires, with random noise added in different ways. The third chapter, an attempt to improve those results, is built upon the cluster expansion method, a technique from statistical mechanics. Exponential ergodicity is obtained for a class of non-Markovian process with non-regular drift. In the final part, the focus shifts onto a stochastic system of interacting particles derived from Keller and Segel 2-D parabolicelliptic model for chemotaxis. Existence and weak uniqueness are proven.
In littoral zones of lakes, multiple processes determine lake ecology and water quality. Lacustrine groundwater discharge (LGD), most frequently taking place in littoral zones, can transport or mobilize nutrients from the sediments and thus contribute significantly to lake eutrophication. Furthermore, lake littoral zones are the habitat of benthic primary producers, namely submerged macrophytes and periphyton, which play a key role in lake food webs and influence lake water quality. Groundwater-mediated nutrient-influx can potentially affect the asymmetric competition between submerged macrophytes and periphyton for light and nutrients. While rooted macrophytes have superior access to sediment nutrients, periphyton can negatively affect macrophytes by shading. LGD may thus facilitate periphyton production at the expense of macrophyte production, although studies on this hypothesized effect are missing.
The research presented in this thesis is aimed at determining how LGD influences periphyton, macrophytes, and the interactions between these benthic producers. Laboratory experiments were combined with field experiments and measurements in an oligo-mesotrophic hard water lake.
In the first study, a general concept was developed based on a literature review of the existing knowledge regarding the potential effects of LGD on nutrients and inorganic and organic carbon loads to lakes, and the effect of these loads on periphyton and macrophytes. The second study includes a field survey and experiment examining the effects of LGD on periphyton in an oligotrophic, stratified hard water lake (Lake Stechlin). This study shows that LGD, by mobilizing phosphorus from the sediments, significantly promotes epiphyton growth, especially at the end of the summer season when epilimnetic phosphorus concentrations are low. The third study focuses on the potential effects of LGD on submerged macrophytes in Lake Stechlin. This study revealed that LGD may have contributed to an observed change in macrophyte community composition and abundance in the shallow littoral areas of the lake. Finally, a laboratory experiment was conducted which mimicked the conditions of a seepage lake. Groundwater circulation was shown to mobilize nutrients from the sediments, which significantly promoted periphyton growth. Macrophyte growth was negatively affected at high periphyton biomasses, confirming the initial hypothesis.
More generally, this thesis shows that groundwater flowing into nutrient-limited lakes may import or mobilize nutrients. These nutrients first promote periphyton, and subsequently provoke radical changes in macrophyte populations before finally having a possible influence on the lake’s trophic state. Hence, the eutrophying effect of groundwater is delayed and, at moderate nutrient loading rates, partly dampened by benthic primary producers. The present research emphasizes the importance and complexity of littoral processes, and the need to further investigate and monitor the benthic environment. As present and future global changes can significantly affect LGD, the understanding of these complex interactions is required for the sustainable management of lake water quality.
Recognizing, understanding, and responding to quantities are considerable skills for human beings. We can easily communicate quantities, and we are extremely efficient in adapting our behavior to numerical related tasks. One usual task is to compare quantities. We also use symbols like digits in numerical-related tasks. To solve tasks including digits, we must to rely on our previously learned internal number representations.
This thesis elaborates on the process of number comparison with the use of noisy mental representations of numbers, the interaction of number and size representations and how we use mental number representations strategically. For this, three studies were carried out.
In the first study, participants had to decide which of two presented digits was numerically larger. They had to respond with a saccade in the direction of the anticipated answer. Using only a small set of meaningfully interpretable parameters, a variant of random walk models is described that accounts for response time, error rate, and variance of response time for the full matrix of 72 digit pairs. In addition, the used random walk model predicts a numerical distance effect even for error response times and this effect clearly occurs in the observed data. In relation to corresponding correct answers error responses were systematically faster. However, different from standard assumptions often made in random walk models, this account required that the distributions of step sizes of the induced random walks be asymmetric to account for this asymmetry between correct and incorrect responses.
Furthermore, the presented model provides a well-defined framework to investigate the nature and scale (e.g., linear vs. logarithmic) of the mapping of numerical magnitude onto its internal representation. In comparison of the fits of proposed models with linear and logarithmic mapping, the logarithmic mapping is suggested to be prioritized.
Finally, we discuss how our findings can help interpret complex findings (e.g., conflicting speed vs. accuracy trends) in applied studies that use number comparison as a well-established diagnostic tool. Furthermore, a novel oculomotoric effect is reported, namely the saccadic overschoot effect. The participants responded by saccadic eye movements and the amplitude of these saccadic responses decreases with numerical distance.
For the second study, an experimental design was developed that allows us to apply the signal detection theory to a task where participants had to decide whether a presented digit was physically smaller or larger. A remaining question is, whether the benefit in (numerical magnitude – physical size) congruent conditions is related to a better perception than in incongruent conditions. Alternatively, the number-size congruency effect is mediated by response biases due to numbers magnitude. The signal detection theory is a perfect tool to distinguish between these two alternatives. It describes two parameters, namely sensitivity and response bias. Changes in the sensitivity are related to the actual task performance due to real differences in perception processes whereas changes in the response bias simply reflect strategic implications as a stronger preparation (activation) of an anticipated answer. Our results clearly demonstrate that the number-size congruency effect cannot be reduced to mere response bias effects, and that genuine sensitivity gains for congruent number-size pairings contribute to the number-size congruency effect.
Third, participants had to perform a SNARC task – deciding whether a presented digit was odd or even. Local transition probability of irrelevant attributes (magnitude) was varied while local transition probability of relevant attributes (parity) and global probability occurrence of each stimulus were kept constantly. Participants were quite sensitive in recognizing the underlying local transition probability of irrelevant attributes. A gain in performance was observed for actual repetitions of the irrelevant attribute in relation to changes of the irrelevant attribute in high repetition conditions compared to low repetition conditions. One interpretation of these findings is that information about the irrelevant attribute (magnitude) in the previous trial is used as an informative precue, so that participants can prepare early processing stages in the current trial, with the corresponding benefits and costs typical of standard cueing studies.
Finally, the results reported in this thesis are discussed in relation to recent studies in numerical cognition.
Natural products and their derivatives have always been a source of drug leads. In particular, bacterial compounds have played an important role in drug development, for example in the field of antibiotics. A decrease in the discovery of novel leads from natural sources and the hope of finding new leads through the generation of large libraries of drug-like compounds by combinatorial chemistry aimed at specific molecular targets drove the pharmaceutical companies away from research on natural products. However, recent technological advances in genetics, bioinformatics and analytical chemistry have revived the interest in natural products. The ribosomally synthesized and post-translationally modified peptides (RiPPs) are a group of natural products generated by the action of post-translationally modifying enzymes on precursor peptides translated from mRNA by ribosomes. The great substrate promiscuity exhibited by many of the enzymes from RiPP biosynthetic pathways have led to the generation of hundreds of novel synthetic and semisynthetic variants, including variants carrying non-canonical amino acids (ncAAs). The microviridins are a family of RiPPs characterized by their atypical tricyclic structure composed of lactone and lactam rings, and their activity as serine protease inhibitors. The generalities of their biosynthetic pathway have already been described, however, the lack of information on details such as the protease responsible for cleaving off the leader peptide from the cyclic core peptide has impeded the fast and cheap production of novel microviridin variants. In the present work, knowledge on leader peptide activation of enzymes from other RiPP families has been extrapolated to the microviridin family, making it possible to bypass the need of a leader peptide. This feature allowed for the exploitation of the microviridin biosynthetic machinery for the production of novel variants through the establishment of an efficient one-pot in vitro platform. The relevance of this chemoenzymatic approach has been exemplified by the synthesis of novel potent serine protease inhibitors from both rationally-designed peptide libraries and bioinformatically predicted microviridins. Additionally, new structure-activity relationships (SARs) could be inferred by screening microviridin intermediates. The significance of this technique was further demonstrated by the simple incorporation of ncAAs into the microviridin scaffold.
During the course of millions of years, evolutionary forces have shaped the current distribution of species and their genetic variability, by influencing their phylogeny, adaptability and probability of survival. Southeast Asia is an extraordinary biodiverse region, where past climate events have resulted in dramatic changes in land availability and distribution of vegetation, resulting likewise in periodic connections between isolated islands and the mainland. These events have influenced the way species are distributed throughout this region but, more importantly, they influenced the genesis of genetic diversity. Despite the observation that a shared paleo-history resulted in very diverse species phylogeographic patterns, the mechanisms behind these patterns are still poorly understood.
In this thesis, I investigated and contrasted the phylogeography of three groups of ungulate species distributed within South and Southeast Asia, aiming to understand what mechanisms have shaped speciation and geographical distribution of genetic variability. For that purpose, I analysed the mitogenomes of historical samples, in order to account for populations from the entire range of species distributions – including populations that no longer exist. This thesis is organized in three manuscripts, which correspond to the three investigated groups: red muntjacs, Rusa deer and Asian rhinoceros.
Red muntjacs are a widely distributed species and occur in very different habitats. We found evidence for gene-flow among populations of different islands, indicative of their ability to utilize the available land corridors. However, we described also the existence of at least two dispersal barriers that created population differentiation within this group; one isolated Sundaic and Mainland populations and the second separated individuals from Sri Lanka.
Second, the two Rusa species investigated here revealed another consequence of the historical land connections. While the two species were monophyletic, we found evidence of hybridisation in Java, facilitated by the expansion of the widespread sambar, Rusa unicolor. Consequently, I found that all the individuals of Javan deer, R. timorensis which were transported to the east of Sundaland by humans, to be of hybrid descent.
In the last manuscript, we were able to include samples from the extinct mainland populations of both Sumatran and Javan rhinoceros. The results revealed a much higher genetic diversity of the historical populations than ever reported for the contemporaneous survivors. Their evolutionary histories revealed a close relationship to climatic events of the Pleistocene but, more importantly, point out the vast extent of genetic erosion within these two endangered species.
The specific phylogeographic history of the species showed some common patters of genetic differentiation that could be directly linked to the climatic and geological changes on the Sunda Shelf during the Pleistocene. However, by contrasting these results I discussed that the same geological events
did not always result in similar histories. One obvious example was the different permeability of the land corridors of Sundaland, as the ability of each species to utilize this newly available land was directly related to their specific ecological requirements. Taken together, these results have an important contribution to the general understanding of evolution in this biodiversity hotspot and the main drivers shaping the distribution of genetic diversity, but could also have important consequences for taxonomy and conservation of the three investigated groups.
All life-sustaining processes are ultimately driven by thousands of biochemical reactions occurring in the cells: the metabolism. These reactions form an intricate network which produces all required chemical compounds, i.e., metabolites, from a set of input molecules. Cells regulate the activity through metabolic reactions in a context-specific way; only reactions that are required in a cellular context, e.g., cell type, developmental stage or environmental condition, are usually active, while the rest remain inactive. The context-specificity of metabolism can be captured by several kinds of experimental data, such as by gene and protein expression or metabolite profiles. In addition, these context-specific data can be assimilated into computational models of metabolism, which then provide context-specific metabolic predictions.
This thesis is composed of three individual studies focussing on context-specific experimental data integration into computational models of metabolism. The first study presents an optimization-based method to obtain context-specific metabolic predictions, and offers the advantage of being fully automated, i.e., free of user defined parameters. The second study explores the effects of alternative optimal solutions arising during the generation of context-specific metabolic predictions. These alternative optimal solutions are metabolic model predictions that represent equally well the integrated data, but that can markedly differ. This study proposes algorithms to analyze the space of alternative solutions, as well as some ways to cope with their impact in the predictions.
Finally, the third study investigates the metabolic specialization of the guard cells of the plant Arabidopsis thaliana, and compares it with that of a different cell type, the mesophyll cells. To this end, the computational methods developed in this thesis are applied to obtain metabolic predictions specific to guard cell and mesophyll cells. These cell-specific predictions are then compared to explore the differences in metabolic activity between the two cell types. In addition, the effects of alternative optima are taken into consideration when comparing the two cell types. The computational results indicate a major reorganization of the primary metabolism in guard cells. These results are supported by an independent 13C labelling experiment.