Hyper-Raman-Streuung folgt anderen Symmetrieauswahlregeln als Raman-Streuung und profitiert als nicht-linearer Zweiphotonenprozess noch mehr von verstärkten elektromagnetischen Feldern an der Oberfläche plasmonischer Nanostrukturen. Damit könnte die oberflächenverstärkte Hyper-Raman-Streuung (SEHRS) praktische Bedeutung in der Spektroskopie erlangen. Durch die Kombination von SEHRS und oberflächenverstärkter Raman-Streuung (SERS) können komplementäre Strukturinformationen erhalten werden. Diese eignen sich aufgrund der Lokalisierung der Verstärkung auf die unmittelbare Umgebung der Nanostrukturen besonders für die Charakterisierung der Wechselwirkung zwischen Molekülen und Metalloberflächen. Ziel dieser Arbeit war es, ein tieferes Verständnis des SEHRS-Effekts zu erlangen und dessen Anwendbarkeit für analytische Fragestellungen einzuschätzen. Dazu wurden SEHRS-Experimente mit Anregung bei 1064 nm und SERS-Experimente mit Anregung bei derselben Wellenlänge sowie mit Anregung bei 532 nm - für eine Detektion von SEHRS und SERS im gleichen Spektralbereich - durchgeführt. Als Beispiel für nicht-resonante Anregung wurden die vom pH-Wert abhängigen SEHRS- und SERS-Spektren von para-Mercaptobenzoesäure untersucht. Mit diesen Spektren wurde die Wechselwirkung verschiedener Silbernanostrukturen mit den Molekülen charakterisiert. Anhand von beta-Carotin wurden Einflüsse von Resonanzverstärkung im SEHRS-Experiment durch die gleichzeitige Anregung eines molekularen elektronischen Übergangs untersucht. Dabei wurde durch eine Thiolfunktionalisierung des Carotins eine intensivere Wechselwirkung mit der Silberoberfläche erzielt, sodass nicht nur resonante SEHRS- und SERS-Spektren, sondern auch nicht-resonante SERS-Spektren von Carotin erhalten werden konnten. Die Anwendbarkeit von SEHRS für hyperspektrale Kartierung in Verbindung mit Mikrospektroskopie wurde durch die Untersuchung von Verteilungen verschiedener Farbstoffe auf strukturierten plasmonischen Oberflächen demonstriert. / Hyper-Raman scattering follows different symmetry selection rules than Raman scattering and, as a non-linear two-photon process, profits even more than Raman scattering from enhanced electromagnetic fields at the surface of plasmonic nanostructures. Surface-enhanced hyper-Raman scattering (SEHRS) could thus gain practical importance for spectroscopy. The combination of SEHRS and surface-enhanced Raman scattering (SERS) offers complementary structural information. Specifically, due to the localization of the enhancement to the close proximity of the nanostructures, this information can be utilized for the characterization of the interaction between molecules and metal surfaces. The aim of this work was to increase the understanding of the SEHRS effect and to assess its applicability to answer analytical questions. For that purpose, SEHRS experiments with excitation at 1064 nm and SERS experiments with excitation at the same wavelength, as well as with excitation at 532 nm - to detect SEHRS and SERS in the same spectral region - were conducted. As an example for non-resonant excitation, pH-dependent SEHRS and SERS spectra of para-mercaptobenzoic acid were examined. Based on these spectra, the interaction of different silver nanostructures with the molecules was characterized. beta-Carotene was used to study the influence of resonance enhancement by the excitation of a molecular electronic transition during SEHRS experiments. By the thiol-functionalization of carotene, a more intense interaction with the silver surface was achieved, which enables to obtain not only resonant SEHRS and SERS but also non-resonant SERS spectra of carotene. Hyperspectral SEHRS imaging in combination with microspectroscopy was demonstrated by analyzing the distribution of different dyes on structured plasmonic surfaces.

Text in English / This thesis investigates the relationship between humans and the nonhuman world or natural environment in selected literary works by black female writers in colonial and post-colonial Namibia and Zimbabwe. Some Anglo-American scholars have argued that many African writers have resisted the paradigms that inform much of global ecocriticism and have responded to it weakly. They contend that African literary feminist studies have not attracted much mainstream attention yet mainly to raise some issues concerning ecologically oriented literary criticism and writing. Given this unjust criticism, the study posits that there has been a growing interest in ecocriticism and ecofeminism in literary works by African writers, male and female, and they have represented the social, political (colonial and anti-colonial) and economic discourse in their works. The works critiqued are Tsitsi Dangarembga’s Nervous Conditions (1988) and The Book of Not (2006), Neshani Andreas’ The Purple Violet of Oshaantu (2001) and No Violet Bulawayo’s We Need New Names (2013). The thrust of this thesis is to draw interconnections between man’s domination of nature and the subjugation and dominance of black women as depicted in different creative works. The texts in this study reveal that the existing Anglo-American framework used by some scholars to define ecocriticism and ecofeminism should open up and develop debates and positions that would allow different ways of reading African literature. The study underscored the possibility of black female creative works to transform the definition of nature writing to allow an expansion and all encompassing interpretation of nature writing. Contrary to the claims by Western scholars that African literature draws its vision of nature writing from the one produced by colonial discourse, this thesis argues that African writers and scholars have always engaged nature and the environment in multiple discourses. This study breaks new ground by showing that the feminist aspects of ecrocriticism are essential to cover the hermeneutic gap created by their exclusion. On closer scrutiny, the study reveals that African women writers have also addressed and highlighted issues that show the link between African women’s roles and their environment. / English Studies / D. Litt. et Phil. (English)

Indiana University-Purdue University Indianapolis (IUPUI) / The purpose of this study was to evaluate the fracture resistance of three post and core systems in endodontically treated teeth by loading to failure, and to measure marginal gaps before and after cyclic loading. Sixty extracted canines were assigned to three groups. The groups tested were: 1) Single cast post and core (Group CP). 2) Prefabricated metal post and composite resin core (Group MR). 3) Glass fiber post and composite resin core (Group FR). All teeth were obturated and prepared to receive a post and core with a coping. Thirty teeth (10 from each group) were loaded to failure, and the other 30 teeth were fatigue-loaded. The marginal gaps on the facial and lingual surface of the fatigue-loaded group were measured before and after cyclic loading. There were two hypotheses for this study. The first was that the FR group would have less marginal gap opening on the lingual surface than the other groups. The second was that the CP group would have a higher load at failure than the other groups. Group CP was found to have a significantly smaller pre-loading marginal gap than group FR (p = 0.0265) and group MR (p = 0.0273), while groups FR and MR did not have a significantly different pre-loading marginal gaps (p = 0.86). Group FR had significantly less change in marginal gap than group MR (p = 0.0013). Groups CP and MR did not have significantly different changes in marginal gap (p = 0.09). Groups CP and FR did not have significantly different changes in marginal gap (p = 0.11). The three post types did not have significantly different maximum loads to failure (p= 0.49), moments of inertia at cervical area (p = 0.75), or moments of inertia at fracture site (p=0.12). There was no significant difference between groups CP, FR, and MR in the load-to-failure test. Group CP demonstrated the highest load-to-failure values; however, the highest load-to-failure mean was for group MR. All fractures observed in this study were catastrophic. Group FR demonstrated better stress distribution and caused no early fractures in the fatigue-loading group. All groups demonstrated significant marginal gap changes on the lingual surface after fatigue loading; however, group FR demonstrated <45 μm marginal gap opening. In group FR, the reduced marginal gap opening was attributed to the use of Panavia 21 with the proper surface treatments to bond to the tooth structure, the resin composite, and the metal coping.

No Abstract Provided / Thesis / Bachelor of Arts (BA)