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Density functional theory (DFT), a powerful toolbox, can unveil chemical transformations in detail. This dissertation focuses on exploring catalytic puzzles, deciphering experimental results, and occasionally, reevaluating conventional concepts. In the first problem, a combination of DFT and kinetic studies uncovers the hidden role of borane in directed borylation reactions catalyzed by iridium complex. Borane, initially considered a side product, is revealed to be an autocatalyst. Chiral catalysts are pivotal for achieving asymmetric molecular construction. However, when the chirality center in the catalyst changes with each turnover, what impact does this have? In our second investigation, we delved into a thorough mechanistic study of enantiomeric selectivity during ruthenium complex-catalyzed hydroarylation. This study leads to a reevaluation and refinement of our concepts of asymmetric induction, specifically tailored to dynamic chirality. A series of six Ni(II) complexes featuring N-heterocyclic carbene (NHC) ligands demonstrate photocatalytic CO2 reduction to CO. Remarkably, these complexes retain their activity even in the absence of a photosensitizer, exhibiting self-sensitized photocatalytic capabilities. Our investigation involved ultrafast transient absorption spectroscopy (TAS) experiments and computational studies to provide a deeper understanding of these catalytic activities. Throughout my PhD journey at Mississippi State University, I engaged in diverse research areas within the chemistry department. The final chapter presents a series of chemistry problems encountered in the Hand Lab, where the application of DFT offers insightful solutions. These problems emerged from discussions and collaborations among graduate students, reflecting the spirit of teamwork and collective problem-solving in the department: 1. Understanding electronic structure of FAVE polymer (Smith lab); 2. Explaining the unexpected isomerization of RhCl(3-Si,Si,P) complex (Montiel lab); 3. Understanding stable dinitrogen pincer abnormal CCCPt(N2) complex (Hollis lab) and 4. Characterization of Ni tripodal PE (E = Si, Ge) complexes and studies on the hydroboration mechanism (Montiel lab)

ITC/USA 2008 Conference Proceedings / The Forty-Fourth Annual International Telemetering Conference and Technical Exhibition / October 27-30, 2008 / Town and Country Resort & Convention Center, San Diego, California / White Sands Missile Range is the largest overland test range in North America occupying over 3,200 square miles in Southern New Mexico and nearby territory. One of the most critical test elements at White Sand Missile Range is it's capabilities in the telemetry field. Much significant advancement in technology has given WSMR and the entire electronics world the ability to achieve new levels of data acquisition that were not achievable a decade ago. And as attention to our nation's defense is of high priority, White Sands Missile Range provides to highest levels of telemetry competence in the Western Hemisphere.

L'etude et la comprehension de phenomenes naturels qu'il<br />semble difficile de predire, tels les<br />tremblements de terre et les raz de maree intriguent depuis quelques<br />temps un certain nombre de physiciens. En effet, il semble que les<br />modeles classiques bases sur des fonctions d'etat continues<br />peuvent difficilement expliquer les phenomenes observes.<br /><br />En 1987, Bak, Tang et Wiesenfeld introduisent un modele base<br /> sur un automate particulier dont l'etude experimentale montre<br /> des caracteristiques proches de celles observees pour des<br /> tremblements de terre. Cet automate est appele automate du tas de sable.<br /><br /> En 1990, Dhar, Ruelle, Sen et<br />Verma etudient les proprietes mathematiques<br />de l'automate du tas de sable. Cet article jette les bases d'une théorie algebrique et combinatoire des<br />etats critiques du systeme en montrant que ceux-ci forment un<br />groupe abelien fini.<br /><br />Cette these porte essentiellement sur l'etude de ce groupe d'un<br />point de vue algorithmique, combinatoire et algebrique. Nous<br />etudions dans un premier temps la complexite de l'operateur de<br />groupe. Puis nous etudions le groupe sur quelques familles de<br />graphes connues avant de montrer que le groupe d'un graphe planaire<br />est isomorphe au groupe de chacun de ses duaux geometriques.<br /><br />Nous montrons comment associer à un groupe abelien fini un<br />idéal de polynomes et dans le cas du groupe du Tas de Sable, nous<br />donnerons une caracterisation de l'operateur de groupe en terme de<br />reduction de polynome.

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Thesis (M.Sc.)--University of Melbourne, Dept. of Science, 1974. / Typescript (roneo copy). Includes bibliographical references (leaves 104-105).

Thesis (M.A.)--University of Adelaide, Dept. of History, 1968. / Includes bibliography.

Análisis jurídico procesal e implicancias comerciales en ámbito deportivo: caso de jugador profesional con resultado positivo en prueba antidopaje.

Alexithymia is a multidimensional psychiatric construct indicating impaired emotional awareness. Its main features are (i) difficulties in identifying feelings and distinguishing them from bodily sensations, (ii) difficulties describing feelings to others, (iii) an externally oriented style of thinking, and (iv) a poor imaginal capacity. Alexithymia attracts great attention among practitioners and researchers in the clinical field because it has the potential to unveil the emotional disturbances occurring in several mental and physical diseases. As has recently been shown, most of these diseases are not only characterized by an altered perception of emotional states but, more generally, by an altered perception of internal bodily states, namely an altered interoceptive awareness. Consequently, a large body of research has focused on the interplay between alexithymia and interoceptive deficits. Yet, the extent of their association is to date unclear. This question is coupled with a further one concerning whether all or just a few features of alexithymia have clinical relevance and/or an association with interoceptive deficits. Indeed, differences in interoceptive ability are not the only candidate to explain differences in emotional awareness. Rather, the sociocultural environment the individual is surrounded by might play a role at least in the way emotions are expressed, but also in the way emotions are felt. This thesis considers both the mentioned issues, thus addressing the relationship that alexithymia entertains with interoceptive abilities on the one hand and with sociocultural factors on the other. I call these, respectively, the embodied and the embedded aspects of alexithymia. This manuscript is articulated in four parts. Part I introduces alexithymia and shows how the operationalization of the construct through time has facilitated the broadening of its conceptual nucleus. Part II focuses on the embodied aspect of alexithymia, namely its relationship with interoceptive deficits. This section outlines results from two empirical studies testing the association between alexithymia and self-reported interoceptive awareness across three large nationality samples. Part III examines the embedded aspect of alexithymia, namely its relationship with sociocultural factors. Together these studies show that (1) interoceptive deficits are a core component of alexithymia, although the latter cannot be reduced to the former, and (2) differences in externally–oriented thinking are empirically predicted by sociocultural factors more than by self-reported interoceptive awareness, even within the same ethnocultural group. In the fourth and last part, a general discussion summarizes the contribution of this work, raising criticisms regarding the current operationalization of alexithymia and the misunderstandings it can cause, especially when combined with a fallacious interpretation of nosological categories. The thesis concludes with the suggestion that adopting a stricter conception of alexithymia and analyzing the interplay between its interoceptive and cognitive subcomponents is beneficial for both emotion theory and clinical practice.

O presente estudo teve por objetivo avaliar os efeitos da administração intramuscular de alfa-tocoferol (vitamina E) sobre marcadores de estresse fisiológico e oxidativo, além de características relacionadas à qualidade da carne de cordeiros submetidos a transporte rodoviário de curta duração. Vinte e quatro cordeiros, mestiços das raças Santa Inês e Dorper, com idade e peso vivo médios ao abate de 138 dias e 43,6 kg, respectivamente, foram distribuídos em três grupos experimentais nos quais receberam, aos seis e três dias antes do transporte, pela via intramuscular, uma aplicação de solução fisiológica; 10 UI; ou 20 UI de acetato de DL-alfa-tocoferol, por quilo de peso metabólico. O transporte teve duração de quatro horas e na chegada ao abatedouro, os cordeiros desembarcaram em curral de espera, onde permaneceram por 19 horas até o momento do abate. Nos momentos T0 (imediatamente antes do embarque e transporte); T1 (imediatamente após transporte e desembarque); T2 (três horas após transporte e desembarque) e T3 (imediatamente antes do abate) foi aferida a temperatura retal e coletadas amostras de sangue por punção da veia jugular para determinação das concentrações séricas de ureia, creatinina, albumina, proteína total, colesterol e cortisol; concentrações plasmáticas de glicose, beta-hidroxibutirato (BHB), lactato e ácidos graxos não esterificados (AGNE); atividade sérica da creatinofosfoquinase (CK); contagem de hemácias e leucócitos totais; relação neutrófilos:linfócitos; volume globular (VG); atividades eritrocitárias da superóxido dismutase (SOD), glutationa peroxidase (GPx) e glutationa redutase (GR); concentração de glutationa reduzida (GSH); status antioxidante total do soro (TAS) e concentração de substâncias reativas ao ácido tiobarbitúrico (TBARS). Após o abate, as carcaças foram mantidas por 24 horas sob refrigeração a 2°C para que pudessem ser determinados o pH (pH24h) e coloração (L*, a*, b*) do músculo Longissimus dorsi, além de coletadas amostras para posterior avaliação da força de cisalhamento (FC), perdas de peso por cozimento (PPC) e produtos da oxidação lipídica após 30 dias de congelamento (TBARS 30). Houve efeito de interação entre momento e tratamento para lactato, sendo observado efeito linear de tratamento no momento T2, com maiores (P= 0,0111) valores dessa variável nos animais que receberam 20 UI de vitamina E. Ocorreu efeito linear de tratamento (P=0,0149) sobre os valores de TAS. Foi observado efeito de desvio da linearidade para albumina, L* e b*. Animais que receberam 10 UI de vitamina E apresentaram menores concentrações de albumina (P= 0,0447) e maiores valores (P=0,0042 e P=0,0082) de L* e b*. Com exceção da temperatura retal e GR, foi observado efeito de momento para todos os outros marcadores de estresse fisiológico e oxidativo. O transporte rodoviário de curta duração, mesmo quando realizado de maneira adequada, gera estresse nos animais. Estímulos potencialmente nocivos no momento prévio ao abate levaram a estresse de maior intensidade que aquele oriundo do transporte. A administração intramuscular de alfa-tocoferol aumentou o status antioxidante total do soro de cordeiros submetidos a transporte rodoviário de curta duração, entretanto não foi capaz de minimizar as alterações decorrentes do estresse fisiológico e oxidativo e de melhorar a qualidade da carne destes animais. / The present study aimed to evaluate the effects of intramuscular alpha-tocopherol (vitamin E) administration on markers of oxidative and physiological stress, as well characteristics related to meat quality of lambs subjected to road short transport. Twenty-four lambs, Santa Inês and Dorper crossbred, age and average live weight at slaughter of 138 days and 43.6 kg, respectively, were divided into three experimental groups. Each group received an intramuscular application of saline solution or 10 IU or 20 IU of DL-alpha-tocopherol per kg of metabolic body weight at six and three days before transportation. The transportation lasted four hours until the slaughterhouse. After unloading, lambs rested in pen for 19 hours until the time of slaughter. At T0 (immediately prior to boarding and transportation), T1 (immediately after transport and unloading), T2 (three hours after transporting and landing) and T3 (immediately before slaughter) rectal temperature was measured and blood samples were collected by jugular vein puncture for determination of serum urea, creatinine, albumin, total protein, cholesterol and cortisol; plasma concentrations of glucose, beta-hydroxybutyrate (BHB), lactate and non-esterified fatty acids (NEFA); serum activities of aspartate aminotransferase (AST), gamma-glutamyl transferase (GGT) and creatine kinase (CK), erythrocyte and total leukocyte count, ratio neutrophil: lymphocytes, packed cell volume (PCV), erythrocyte activities of superoxide dismutase (SOD), glutathione peroxidase (GPx) and glutathione reductase (GR), concentration of reduced glutathione (GSH), serum total antioxidant status (TAS) and the concentration of thiobarbituric acid reactive substances (TBARS). After slaughter, carcasses were kept for 24 hours under refrigeration at 2 °C and were analyzed for Longissimus Dorsi pH (pH24h) and color (L *, a *, b *), and collected samples for subsequent evaluation of shear force (SF), cooking weight loss (CWL) and products of lipid oxidation after 30 days of freezing (TBARS 30). There was an interaction between time and treatment for lactate and was observed a linear effect at the time T2, with increased (P = 0.0111) values of this variable in the animals receiving 20 IU of vitamin E. A linear effect of treatment (P = 0.0149) on the TAS values was observed. Deviation from linearity effect for albumin, L * and b * were seen. Animals that received 10 IU of vitamin E showed lower concentrations of albumin (P = 0.0447) and higher (P = 0.0042 and P = 0.0082) L * and b * values. Except for rectal temperature and GR, moment effect was observed for all other markers of oxidative and physiological stress. The short road transportation, even when done properly, produces stress in animals. Potentially harmful stimuli at the time prior to slaughter led to higher stress intensity than that coming from the transport. Intramuscular administration of alpha-tocopherol increased serum total antioxidant status of lambs subjected to short duration road transport, however was not able to minimize changes arising from physiological and oxidative stress and improve the meat quality of these animals.