This work involves the development of novel organic methodology utilizing the principles of green chemistry and exclusively in environmentally benign solvents. The methodologies are developed in two different areas, namely the direct formation of tetrahydropryanols in both ionic liquid and water and C-X activation in aqueous media The development of methodologies for direct tetrahydropyranol derivatives synthesis was completed in both ionic liquid and water. In the method that utilized ionic liquid as the solvent, the ionic liquid used was butylmethylimidazolium hexafluorophosphate, [bmim][PF6], in which a simple homoallyl alcohol and an aldehyde reacted in the presence of a catalytic amount of cerium triflate hydrate to yield the exclusive formation of tetrahydropyranol derivatives. In the method that utilized water as the solvent, the acid source used was Amberlite IR-120RTM Plus resin, which has a sulfonic acid moiety. In the presence of the resin and under sonication in water, a simple homoallyl alcohol and an aldehyde yields the direct formation of tetrahydropyranol derivatives in water Various factors have limited the extension of the aqueous methodology onto nonactivated C-X bonds and have been limited to activated C-X bonds such as allyl halides. Therefore, the overall goal of the C-X activation project was to develop an environmentally friendly, aqueous solvent based novel methodology that would allow for the addition of nonactivated simple alkyl halides onto the appropriate electrophilic system. We started from the relatively facile addition of an unactivated alkyl halide to a 1,4-unsaturated system, using electron-deficient alpha-phthalimidoacrylate derivates, to form alpha-amino acid derivatives. The next stage involved the addition of unactivated alkyl halides to alpha-imino esters to form alpha-amino acid derivatives, followed by the addition to an imine to form amine derivatives. The culmination of the project was also the most difficult and resulted in the first report of a high yield Barbier-Grignard type carbonyl alkylation with non-activated halides in water / acase@tulane.edu

acase@tulane.edu

In this dissertation two theoretical models for calculation of solvent-induced vibrational transition probability are introduced. These models are based on Feynman's real-time discretized path integral techniques. In the first model, discretized real-time path integral is applied to a system consisting of a diatomic in a small cluster of two solvent atom. The system considered consists of Br$\sb2$ in Ar. An adiabatic separation of variables is assumed. The solvent as well as the Br$\sb2$ center of mass are gathered into a vector called bath or solvent coordinates. The forced harmonic oscillator approximation is used to analytically obtain the vibrational contribution to the transition amplitude. The discretized real time propagators (bath dependent only, since the vibrational part is carried out analytically) are highly oscillatory and, therefore, not suitable for Monte Carlo calculations. The local averaging technique introduced by Filinov and developed by Freeman and Doll, and Miller and Makri is employed to make the integrands more suitable for a Monte Carlo evaluation (the oscillations are pre averaged before the Monte Carlo procedure is applied). The computations are carried out for five different times. For each time, we study the convergence of the technique for a range of Gaussian widths used as local averaging functions. We also study convergence as a function of the number of time divisions in the discretized description of the solvent path In the second model, a new approximate technique for real-time discretized path integral simulations are introduced. The technique transforms the oscillatory integrands into non-oscillatory functions for accurate Metropolis Monte Carlo evaluation. The method is applied to the same prototype system of a Br$\sb2$ diatomic in a cluster of solvent atoms. The solvent-induced vibrational transition probability of finding the diatomic in its ground vibrational state is calculated at time t. The diatomic is initially in its first vibrational state. Computations are carried out for two different times and the results are compared to the results of full discretized path integral calculations of the first model. The convergence of the technique is tested as a function of the number of time divisions in the discretized description of each solvent path / acase@tulane.edu

The study assessed the development over a 3-year period of children's ability to differentiate accurately peers' physical, behavioral, and psychological characteristics. Participants were 4 girls and 10 boys (averaging 95.05 months of age at the beginning of the study), first seen when they were in second grade and retested as third and fourth graders. Children were presented with pictures of all possible pair of classmates and were asked to make judgments on their peers' height, tendency to get angry, mathematical and running abilities, and to indicate their liking for classmates. Objective measures of each characteristic were also obtained. Children's differentiating ability and the accuracy of their judgments increased over time. In second grade, only few characteristics were differentiated, all in relation to height; and judgments in general were inaccurate. In third grade, differentiation increased, and children were accurate at judging peers' height. By fourth grade, children differentiated between most characteristics and were accurate at judging height and running speed. Three individual patterns of development at differentiating accurately peers' characteristics were identified, but most children matched the group's normative developmental pattern. Two procedures for analyzing group paired-comparison data were contrasted / acase@tulane.edu

For most chemical reactions, two events are involved: the breaking of the old bond (or bonds) and the formation of the new bond (or bonds). In order to influence the outcome of a reaction, chemists have used many methods to achieve selective cleavage of the targeted bond. In this dissertation, studies on site-specific cleavage of alkyl radicals by excimer lasers are presented and possible practical applications are discussed. The propensity of C-H bond cleavage at the $\beta$ position for small organic radicals such as the ethyl and the n-propyl was observed in the experiment results. A two-color photolysis process was implemented to confirm that the dissociation route unequivocally involves photolysis of a radical intermediate. Markov chain methods have been used to simulate partially the scrambling of the radicals in an effort to gain more insights into the dissociation process. Site-specific research has also been conducted on systems that are relevant to semiconductor manufacturing. Extensions to bimolecular systems are also presented. Here, results of the reaction between chlorine atoms and selectively-deuterated propanes are provided / acase@tulane.edu

acase@tulane.edu

acase@tulane.edu

My major aim in this study will be to trace, by using the theory of hegemony, as ariticulated by Antonio Gramsci and further elaborated by Ernesto Laclou and Chantal Mouffe, the discourse of (inter)nationalism in four nineteenth-century British novels: Waverley (1814), Alton Locke (1850), Phineas Finn (1869), and Daniel Doronda (1876). I will intend to demonstrate how (inter)nationalism, as a form of consciousness generated hegemonically throughout the British society, was always present although not easily detected in the novelistic discourse of the nineteenth century During the nineteenth-century in Great Britain, the novel, as a dialogic discourse resistant to totalizing, played a crucial role in establishing the terms of liberal (inter)nationalism, that is, an uneasy negotiation between nationalism and internationalism. As the dominant textual form of the century, the novel was an interesting unity of contradictory ideologies that refused to be reduced to any particular dominant ideology. Thus, both Marxist and liberal political theories fail to represent themselves as the sole legitimate discourse of the British nation. Be it classified as a historical novel, such as Waverley, an industrial novel, such as Alton Locke , a political novel, such as Phineas Finn, or a realist novel of individual growth, such as Daniel Deronda, the British novel struggles both to construct and solidify British national identity and at the same time it broadens national divisions within. As a result, there becomes obvious a highly problematic and complex relationship between Englishness and Britishness in all the four novels My intention, however, is neither to claim the supremacy of the novel in the artificial creation of Britishness, nor the supremacy of any national identity within the British nation-state but to suggest that the nineteenth-century British novel just like the British nation itself both produced and was a product of a specific national climate of that century. I will attempt to analyze how the four novels, as they struggle to construct an international and multinational discourse, use the very nationalistic discourses that they attempt to escape Nationalism is practiced not only by the dominant nation, but also by the dominated ones. The nineteenth-century British novel, as the most 'national-popular' genre, reflects the contradictory process of nation-formation in which multiple national identities---English, Welsh, Scottish, Irish---were competing against each other while, at the same time, they were being more and more disseminated hegemonically into Englishness/Britishness I will explore the possibility that the British novel during the nineteenth century was in this sense determined by what I call an '(inter)national' consciousness. As the genre that provided a highly productive form of the 'national-popular' discourse that was introduced by Gramsci, the novel reflected this (inter)national consciousness. By discussing Gramsci and various theorists of ideology and nationalism such as Benedict Anderson, Anthony Birch, John Breuilly, Eric Hobsbawm, and Anthony D. Smith, I will demonstrate how hegemony, as a complex interplay of practical factors and discursive practices, turns into the major theoretical tool in the study of such a complex concept that I call '(inter)nationalism.' / acase@tulane.edu

acase@tulane.edu

acase@tulane.edu