Consacrée à l’analyse comparée du Cid (1661) et de La Parodie du Cid (1972), cette thèse porte sur la « relation critique » qui a été établie par le biais de la parodie entre les deux textes. Empruntée à Daniel Sangsue, l’expression met en évidence le fait que la réécriture parodique d’une œuvre n’est pas seulement un exercice de divertissement, mais une manière de réaliser une critique de l’intérieur, dont le résultat n’est pas une étude analytique, mais un texte littéraire. Néanmoins, si la parodie ne se limite pas à faire rire, elle se construit, certes, en contraste avec le texte parodié – le comique étant un élément fondamental de cette relation. Comme, de 1941 à 1972, la PDC a subi des modifications, une analyse comparée des versions est aussi devenue impérative pour notre étude. Dans ce cas, nous avons évalué si les changements effectués par le parodiste au fil des années ont contribué à une lisibilité accrue de la pièce et à son adaptation à un public changeant. Écrite en Algérie française et en pataouète, la PDC a exigé également une mise en place des enjeux spécifiques de la pièce et de son époque. C’est pour cela que les rapports entre colonie et métropole aussi qu’entre les différents composants de l’ordre colonial sont ici convoqués et problématisés. Notre hypothèse est que la PDC est – selon une formulation de Sangsue – une « critique en acte», puisque se rapprochant du modèle cornélien, Brua prend aussi ses distances, produisant un texte nouveau. / Devoted to a comparative analysis of Le Cid (1661) and La Parodie du Cid (1972), this thesis focuses on the "critical relationship" that has been established through parody between the two texts. Borrowed from Daniel Sangsue, the concept of parody highlights the fact that the parodic rewriting of a text is not merely an exercise for entertainment, but a way of performing a critique from within, the result of which is not an analytical study, but a literary text. Nevertheless, if the parody is not limited to making people laugh, it is certainly built in contrast with the parodied text - the comic being a fundamental element of this relationship. As the PDC underwent changes between 1941 and 1972, a comparative analysis of the versions of the play also became imperative for our study. In this case, we assessed whether the changes made by the parodist over the years contributed to the increased readability of the play and its adaptation to a changing audience. Written in French Algeria and in Pataouète, the PDC also required a set of the specific issues of the play and its time. This is why the relationship between the colony and metropolis as well as between the different components of the colonial order is summoned and problematized here. Our hypothesis is that PDC is – according to a formulation of Sangsue – a "critique in act", since approaching the Cornelian model, Brua also distances himself, producing a new text.

This thesis explores the use of mass spectrometry to define the strengths, and understand solution phase speciation of phenolic oxime-based solvent extractants of the types used in the hydrometallurgical recovery of copper. Chapter 1 reviews briefly the current extraction technology for copper and focuses on hydrometallurgy and the use of phenolic oximes such as 5-nonylsalicylaldoxime. The modification of the latter to improve extraction efficiency is discussed, focussing on the introduction of X-substituents in the 3 position of the benzene ring. Modern mass spectrometry techniques are also discussed with a focus on their application to inorganic systems and their use in achieving the aims of this thesis, as defined above. The work described in chapter 2 involves the development of collision induced dissociation (CID) techniques to determine the relative gas phase stabilities of copper complex anions of the type [Cu(L)(L-H)]-, where LH is a 5-alkyl-3-X-2- hydroxybenzaldehyde oximes and X a range of substituents. The importance of interligand interactions in the outer-coordination sphere and their influence on gas phase anion stability, as defined by CID, is reported. The work described in Chapter 2 on CID is extended in chapter 3 and looks at the effect of charge, of ligand type, LH, and of the nature of the metal on the stability of ionic forms of [M(L)2] complexes, where LH is extended to include 5-alkyl-2- hydroxyphenylethanone oximes. The effects of substitution at the azomethine carbon atom and at the 3-position of the benzene ring and of variation of the nature of the metal on the ion dissociation mechanisms are shown to have a major influence on ion stability under CID conditions. In chapter 4 density functional theory calculations have been used to investigate the influences of substitution at the azomethine carbon atom and at the 3-position of the benzene ring and of variation of the nature of the metal on the gas phase structures of the neutral complexes, [M(L)2]. Gas phase deprotonation and dimerisation enthalpies of the ligands, LH, and enthalpies of formation of [M(L)2] complexes have been calculated and correlates with experimentally determined ligand extraction strength. The ligand type has been extended to include 3-X-2-hydroxybenzaldehyde hydrazones, which have previously been shown to have lower distribution coefficients for copper than the analogous 3-X-substituted oximes. The calculated gas phase formation enthalpies for [M(L)2] show a strong correlation with the strengths as extractants LH, measured as their pH0.5 values for metal uptake. Chapter 5 considers whether mass spectrometry can be used to define the solution equilibria when two different oxime-based ligands, LXH and LYH, compete for Cu(II) in a single phase solution. It has been established that shifts in the relative peak intensities of deprotonated ions derived from the Cu(II) complexes, [Cu(LX)2], [Cu(LY)2] and [Cu(LX)(LY)] reflect changes in the solution composition. The work described in chapter 6 extends the study of solution phase speciation using mass spectrometry. When the Cu(II) and proton concentrations of solutions were varied distinct changes in the resulting electrospray mass spectra were observed and the resulting species were identified using CID and high resolution mass spectrometry. A novel, [Cu3(L-H)3-μ3-O/OH]- species is determined to be a major component of solutions where Cu(II) concentrations are equal to/greater than the LH concentration. Various 3-X-2-hydroxybenzaldehyde oximes (X = CH2NR2) were synthesised. The incorporation of a protonatable arm in the 3-position enabled trinuclear complexes, [Cu3(L-H)3-μ3-OH], to be isolated and fully characterized, including two X-ray determined crystal structures.

Corporations as such are often not perceived to have moral agency, and directors and officers of the corporation are frequently not considered responsible for corporate actions. However, I appeal to Peter French's view that reflection on a corporate internal decision (CID) procedure shows that a corporation should be considered a moral agent. Many writers have cast doubt on the correctness of French's view, but I defend it from several major objections.

No description available.

This dissertation investigates Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) based techniques to study the impact of molecular structure on conformation and binding energetics. A novel method to determine collison cross sectional areas using FTICR (CRAFTI), initially developed by the Dearden lab, was applied to study the conformations of molecular systems with unique structural attributes in an attempt to explore the molecular range of CRAFTI. The systems chosen for CRAFTI studies include crown-ether alkylammonium complexes and biogenic amino acids. The results were found to be consistent with expected behavior, and strongly correlated with experimental measurements made using ion mobility spectrometry (IMS) and predictions from computations. The analytical sensitivity of CRAFTI was highlighted by its ability to distinguish the normal and branched structural isomers of butylamine. Besides conformation characterization, quantitative evaluation of binding was undertaken on metal ion-cryptand complexes on the FTICR instrument using sustained off-resonance irradiation-collision-induced dissociation (SORI CID) method. Complex formation and dissociation was found to be a strong function of both guest and host sizes which impacted steric selectivity, and polarizability. The results demonstrate the ability of FTICR to simultaneously determine structure, conformation and binding thereby providing comprehensive molecular characterization.

Mentions of God were omnipresent in the early vernacular texts of thirteenth-century Spain. In this dissertation, I study the mentions of God in three well-known Spanish narrative poems written down in the thirteenth century. These are the Cantar de mio Cid, the Libro de Alexandre, and the Milagros de Nuestra Señora. In particular, I discuss how the representation of God in these works is shaped by each of the three poets' original intended audiences and the message that he wished to communicate to those listeners. I begin by reviewing critical reconstructions of the original intended audiences of the three poems. I then study three aspects of the representation of God in each of the three poems: the words used to reference God, the descriptions of the deity present in the texts themselves, and the roles and functions assigned to God as a character in each narrative. I conclude that the Judeo-Christian God was an expected element in early Spanish narrative poetry, but that his representation could vary widely based on the differing compositions of the audiences for whom the works were conceived. / text

The reversible phosphorylation of proteins plays a key role in nearly every aspect of cell life. This essential post-translational modification controls a myriad of cellular events from cell survival, differentiation, and migration to apoptosis. Two classes of enzymes, kinases and phosphatases, tightly control all phosphorylation events. Perturbation in the activity of any member of these classes of enzymes has been linked to numerous diseases including cancer, metabolic disorders, immune disorders and neurological disorders. Therefore, there is a great interest among the scientific community to develop methods to selectively modulate the activity of kinases and phosphatases not only for therapeutic purposes but also to understand the fundamental role of these enzymes in signaling events. The more than 500 kinases encoded in the human genome share a common catalytic fold and most inhibitors target the ATP binding site. Therefore selective targeting of a single kinase by an inhibitor at the highly conserved ATP binding site is one of the main concerns for designing probes or drugs. Our group has taken advantage of the potency and possible selectivity imparted by bivalent inhibitors and developed an in vitro selection approach to discover bivalent ligands. The strategy involves the use of an ATP-competitive small molecule warhead and a library of cyclic peptides displayed on phage that interact with the kinase of interest in a dynamic selection. The selection for a kinase binding peptide is carried out until consensus peptides are found and bivalent ligands are constructed by linking the selected cyclic peptide with the small molecule warhead through a synthetic linker. Using this approach a potent and selective bivalent inhibitor was found for PKA, a serine/threonine kinase. To interrogate the generality of this approach, a kinase closely related to PKA (PRKX) was used for which a very potent and selective bivalent ligand was found. The same selection strategy was further extended to the two kinases Lyn and Brk, which belong to the tyrosine kinase family. Though peptides were isolated that bound the desired kinase, potent bivalent inhibitors were not discovered. More generally, these experiments in sum are building a library of information regarding how to best design selections of potent and selective bivalent inhibitors. We further explored modulation of the activity of kinases and phosphatases by employing a ligand-gated split-protein approach. The small molecule gated spatial and temporal control of these enzymes should allow the study of signaling events in a controlled manner. The strategy employed consists in the identification of possible fragmentation sites within the catalytic domain of kinases and phosphatases by a sequence dissimilarity approach. Loop insertion mutants at the selected sites were tested for catalytic activity. Successful insertion mutants were further split into two catalytically inactive fragments, which were appended to two conditionally interacting protein domains. Upon addition of a small molecule, the two conditionally interacting domains reassemble the catalytic domain of the enzyme and restore catalytic activity. Using this approach we were able to modulate the activity of the tyrosine kinases Lyn, Fak and Src and the AGC kinase PKA. We also extended the approach to gate the activity of tyrosine phosphatases PTP1B, SHP1 and PTPH1. Finally, these ligand-gated split-kinases and phosphatases were validated in-cellulo. Thus, this work resulted in a new method for designing split-proteins and provided a palette of kinases and phosphatases that can be turned-on by small molecules. In total, these efforts describe two alternative routes that can be used to modulate phosphorylation events in a selective and controlled manner.

When a vehicle enters an intersection with insufficient space to exit on the opposite side the result is often the obstruction of pedestrians and other vehicles, this phenomenon is usually referred to as "blocking the box." The purpose of this study was to determine different characteristics of blocking that might be considered in determining the installment of a "Don't Block the Box" (DBTB) campaign. This study identified potentially problematic intersections in Atlanta, Georgia and collected information, such as the number of vehicles that block the intersection (box junction), the amount of green time with blocking, and the percentages in which approaches were blocked. Based on the results it was found the characteristics of the number of blockers, percentage of green time with blocking, and the percentage of lost capacity are excellent indicators for a possible DBTB campaign. Organizations interested in potentially starting a DBTB should consider these characteristics part of the determination of suitability of DBTB for an intersection. Within this study is was found that the intersections of Peachtree Road & Highland Drive, Peachtree Road & Stratford Road, Peachtree Road & Lenox Mall Entrance, and 10th Street & Williams Street showed to be potential candidates for a DBTB campaign in Atlanta, Georgia. During the study period these intersections had high percentages of lost capacity, high number of blocks, and high percentages of green time with blocking. In conjunction with the DBTB data analysis a "DBTB survey" was developed. The objective of this survey was to help gain a better understanding of the current trends in DBTB campaigns around the United States. The "DBTB Survey" received 75 responses from 415 organizations around the nation, a 18.1% response rate. Six (60%) of the ten participants that currently have a DBTB campaign found a sufficient level of improvement in traffic operations and 46 of the total respondents (60%) proclaimed that if DBTB campaigns were shown to be an economical alternative for traffic management they would consider starting one to help congestion and safety.

Mass spectrometry with electrospray ionization is an excellent method for structural analysis of coordination compounds with outstanding sensitivity and selectivity. However, it fails to detect some low-polar rhenium complexes. This master thesis describes derivatization method of non-ionizable rhenium complexes with 1,2-dihydroxybenzene and 2,3- dihydroxytoluenene. Fragmentation mechanisms and structure of prepared complexes was studied using high resolution mass spectrometry and collision-induced dissociation (CID). Furthermore, density functional theory (DFT) computational method was used for prediction of bond cleavage based on bond lengthening.

In my dissertation, I use a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR-MS) to investigate supramolecules. Cross-sectional areas by Fourier transform ICR (CRAFTI), a novel technique for measurements of collision cross sections by FTICR, is demonstrated for the first time. The CRAFTI method measures the total "dephasing cross section" for removal of the ions from the coherent packet in the FTICR cell, including contributions not only from momentum transfer but also from reactive collisions including those leading to collisional dissociation. Experimental CRAFTI collision cross sections correlate linearly with theoretically computed results and with results obtained using ion mobility measurements. Different collision gases, including Xe, N2, Ar, and SF6, are all appropriate for the CRAFTI technique when the experiments are done at proper kinetic energies. The CRAFTI technique was applied to characterize the molecular shape of complexes of alkyl mono- and n-alkyldiamine with cucurbit[n]uril in the gas phase. The CRAFTI results are consistent with corresponding computational geometries. The CRAFTI technique was combined with SORI-CID (sustained off-resonance irradiation collision induced dissociation) for characterization of complexes of α,ω-alkyldiammonium with cucurbit[n]urils (n=5, 7 and 8) and cucurbituril derivatives. The results demonstrate that for bigger cucurbiturils, the complexes have the alkyldiamine tails threaded through the cavity of the host; for smaller cucurbiturils, the complexes have the tails of the alklydiamines external to the portal of the host.Capping molecules for larger CBn to form larger containers were also investigated. Using SORI-CID methods, CB7, a bigger cucurbituril cage, was found to form a more stable complex with Gu+ (guanidinium). Several neutral guests (benzene, fluorobenzene and toluene) were trapped in CB7 cavity to form inclusion complexes.