Semiempirical Study of the Bergman Reaction: Towards a Computationally Efficient and Accurate Method for Modeling Enediyne Anticancer Antibiotics

Over the past 7 years, the enediyne anticancer antibiotics have been widely studied due to their DNA cleaving ability. The focus of these antibiotics, represented by kedarcidin chromophore, neocarzinostatin chromophore, calicheamicin, esperamicin A, and dynemicin A, is on the enediyne moiety contained within each of these antibiotics. In its inactive form, the moiety is benign to its environment. Upon suitable activation, the system undergoes a Bergman cycloaromatization proceeding through a 1,4-dehydrobenzene diradical intermediate. It is this diradical intermediate that is thought to cleave double-stranded dna through hydrogen atom abstraction. Semiempirical, semiempiricalci, Hartree–Fock ab initio, and mp2 electron correlation methods have been used to investigate the inactive hex-3-ene-1,5-diyne reactant, the 1,4-dehydrobenzene diradical, and a transition state structure of the Bergman reaction. Geometries calculated with different basis sets and by semiempirical methods have been used for single-point calculations using electron correlation methods. These results are compared with the best experimental and theoretical results reported in the literature. Implications of these results for computational studies of the enediyne anticancer antibiotics are discussed.

The Persistence of Shattered Dreams: a Comparative Study of the Audacity of the American Dream

In my thesis, I use historical and literary analysis to study how the concept of the American Dream was popularized during the Great Depression and how cultural understanding of the term has changed following the 2008 Recession. By comparing popular media, literature, and political documents within a historical framework from the 1930s and after 2008 through the present day, I analyze how the term ¿American Dream¿ has persisted as an element of the United States¿ national ethos. I explore why the language of the American Dream does not appear to carry the same resonance in American society as in the 1930s, even though the post-2008 economic environment is somewhat comparable to conditions created by the Great Depression and associated reform measures. This comparative historical approach in scholarly studies of the American Dream is unique because the two periods have not previously been discussed in relation to one another in order to show transformations in cultural understanding of the Dream. The American Dream, both embodying a dual identity as an aspiration to aspire to and also as a delusional fantasy which can lead to cynicism, is a highly complex idea in lived experience. The concept¿s ambiguous nature allows for individuals to interpret it differently, allowing for the term to remain resilient throughout different periods in United States history. While the meaning of the term has been subject to change, it is grounded upon an idealistic concept of American individualism and hope that through one¿s merit, one will be able to achieve one¿s vision of success. Through interdisciplinary analysis, I show that the American Dream will alter to suit the needs of contemporary society and the term¿s power will continue to endure in society despite evidence of rising cynicism since 2008.

Chinese Whiteness: The Discourse Of Race In Modern And Contemporary Chinese Culture

This thesis chronicles the development of western forms of race and racism in China. It then studies contemporary China using theories derived from whiteness studies in order to explain the unique position that whites (Caucasians) have in China today. In Chapter I, I break down the definition of race and introduce a foundation for a whiteness studies approach to research. In Chapter II, I analyze how Chinese classified themselves and other humans prior to the western system of race. In Chapter III, I chronicle the introduction of western forms of race and racism to China, and the appropriation of these concepts to suit Chinese goals. In Chapter IV, I approach cultural phenomenon in contemporary China by situating them in their historical traditions as well as by approaching them as displaying an internalized racism and white privilege. Finally in the Conclusion, I postulate on what China¿s contemporary racial system means for China.