Previous research has indicated that aggression is generally detrimental to performance in the occupational domain (Campbell, 1990; James et al., 2005; Sackett, 2002; Viswesvaran et al., 1999). In certain athletic contexts, however, aggression may serve to enhance performance at the team level. For this analysis, team-level aggression is hypothesized to be positively related to team performance in basketball. Aggression in this context is defined as "the desire to inflict harm on another individual, group, or entity" (James, 2005, p.71). Both implicit (CRT-A) and explicit (NEO-PI-R) aggression were measured, and team performance was represented primarily by team scores. The data demonstrate that team-level implicit aggression is significantly and positively related to team performance, however team-level explicit aggression does not have a significant relationship with team performance.

This thesis examines the synthesis, photophysical properties, and sensory responses of hydroxy-substituted 1,4-distyryl-2,5-bis(arylethynyl)benzenes (Cruciforms, XFs). These two-dimensional cross-conjugated materials possess spatially separated frontier molecular orbitals (FMOs). This spatial separation allows the HOMO and LUMO to be addressed independently by analytes, which leads to significant changes in their absorption and emission. These properties allow XFs to be utilized for the detection of various analytes. These studies highlight the benefits of utilizing XFs for the development of advanced functional solid state materials for sensory applications.

Thèse de doctorat : Informatique : Paris 12 : 2005. Thèse de doctorat : Informatique : Oldenburg, Carl v. Ossietzky Universität : 2005. / Thèse soutenue en co-tutelle. Titre provenant de l'écran-titre. Bibliogr. p. 166173. Index.

The cation&ndash;&pi; interaction has been long-established to play an important role in molecular recognition, supramolecular chemistry, and molecular biology. In contrast, its potential application in small-molecule catalysis, especially as a selectivity-determining factor in asymmetric synthesis has been overlooked until very recently. This dissertation begins with an extensive literature review on the state-of-the-art research on the application of cation&ndash;&pi; interactions in non-enzymatic catalysis of organic and organometallic transformations. The research in this field has been largely inspired and guided by the related biosynthetic systems incorporating the same type of interactions.</p> / Chemistry and Chemical Biology

For several decades, the field of magneto-optics (MO) has demonstrated applications that have impact on every day applications such as in optical data storage, magnetic field sensing, crucial for magnetoencephalography and magnetocardiography; and compact and efficient optical isolators, among others. In the past, many of these applications and the devices designed for them have heavily relied on inorganic materials. Organic materials with a high MO response represent an interesting alternative to the inorganic equivalent by not only being a more cost efficient solution, but also by allowing the user to modify a number of variables to control and optimize the MO performance depending on the application and level of performance desired. In this dissertation I discuss the MO properties of novel organic materials, starting with polythiophene, which has been of interest due to the strong relationship between its high MO performance and its lamellar structure and regioregularity. I will also be discussing another material system that provides several degrees of MO tunability: magnetite based nanocomposites. A unique and novel synthetic approach described in this dissertation yields both highly transparent and MO responsive polymer films. I will be describing a systematic approach that indicates a strong influence of the size of the nanoparticle as well as the nanoparticle concentration in the MO performance of the bulk polymer, while maintaining high optical quality with minimal scattering and absorption in the visible and near infrared. Finally, I will be discussing the implementation of both a magnetite nanocomposite and a cobalt ferrite based nanocomposite in a free space magnetic field system and demonstrate the proof-of-principle operation of a sensing system.

A psi-calculus is an extension of the pi-calculus with nominal data types for data structures, logical assertions, and conditions. These can be transmitted between processes and their names can be statically scoped as in the standard pi-calculus. Expressiveness and therefore modelling convenience significantly exceed those of other formalisms: psi-calculi can capture the same phenomena as other extensions of the pi-calculus, and can be more general, e.g. by allowing structured channels, higher-order formalisms such as the lambda calculus for data structures, and predicate logic for assertions. Ample comparisons to related calculi are provided and a few significant applications are discussed. The labelled operational semantics and definition of bisimulation is straightforward, without a structural congruence. Minimal requirements on the nominal data and logic are established in order to prove general algebraic properties of psi-calculi. The purity of the semantics is on par with the pi-calculus. The theory of weak bisimulation is established, where the tau actions are unobservable. The notion of barb is defined as the output label of a communication action, and weak barbed equivalence is bisimilarity for tau actions and preservation of weak barbs in all static contexts. It is proved that weak barbed equivalence coincides with weak bisimulation equivalence. A symbolic transition system and bisimulation equivalence is presented, and shown fully abstract with respect to bisimulation congruence in the non-symbolic semantics. The symbolic semantics is necessary for an efficient implementation of the calculus in automated tools exploring state spaces, and the full abstraction property means processes are bisimilar in the symbolic setting if they are bisimilar in the original semantics. Psi-calculi remove the necessity of proving general properties every time a new mobile process calculus is defined. By properly instantiating the framework the properties are guaranteed to hold, thus removing the need to do tedious and error-prone proofs.

La presente tesis consta de dos vertientes interrelacionadas. La primera se centra en intentar cuantificar experimentalmente la contribución energética en disolución de la interacción anión-&#61552;, mediante el uso de calix[4]pirroles aril substituidos en las posiciones meso- como moléculas modelo. El trabajo realizado muestra que la interacción anión-&#61552; es repulsiva para anillos con valores de ESP negativos y a medida que el efecto electrón atrayente de los sustituyentes aumenta la interacción se vuelve menos repulsiva, hasta que, cuando el valor de ESP en el centro del anillo aromático es positivo la interacción se vuelve ligeramente atractiva. La segunda en el uso de estos receptores simples para obtener arquitecturas supramoleculares más complejas, y su autoensamblaje en capsulas. Los estudios muestran que calix[4]pirroles sustituidos con grupos urea en sus anillos aromáticos se autoemsamblan en capsulas diméricas en presencia de un huesped adecuado como los N-óxidos de alquil aminas y piridinas en disolventes apolares. / This thesis consists of two interrelated aspects. The first one pretends to quantify experimentally the energetic contribution in solution of the anion-&#61552; interaction, using aryl extended calix[4] pyrroles substituted in their meso- positions as a model system. The work performed shows that the anion-&#61552; interaction is repulsive for aromatic rings with negative ESP values, as the electron withdrawing character of the substituent increases the interaction becomes less repulsive, until eventually, when the ESP value in the center of the aromatic ring is positive the interaction turns into slightly attractive.The second one is based on the use of these simple receptors as scaffolds to obtain complex structures and their self-assembly into capsules. The studies performed show that aryl extended calix[4]pyrroles substituted with urea functions on their upper rim self-assemble into dimeric capsules in the presence of a suitable guest like the N-oxides of alkyl amines and pyridines in non-polar solvents.

The purpose of this thesis was to determine whether the NEO Personality Inventory-Revised (NEO PI-R) could account for significant variance within a measure of personality developed for the intellectually disabled (i.e., the Reiss Profile of Fundamental Motives), as well as to consider their comparative validity. The NEO PI-R and the Reiss Profile of Fundamental Motives were administered to 127 undergraduate students in conjunction with the Personality Research Form (PRF) and the Behavior Report Form (BRF). The NEO PI-R was able to account for a substantial amount of variance in the Reiss Profile scales, and the Reiss and the NEO accounted for approximately equivalent amounts of variance in the PRF and BRF. Implications for general personality research as well as additional research with a sample of adults with intellectual disability are discussed.

The field of organic electronics has received much attention over the last few years, and engineering of organic crystals to grow with pi-electron systems arranged in a face-to-face motif has been shown to be beneficial in electronic devices. The effects of combining aromatic and perfluorinated aromatic derivatives have shown that the intramolecular stacking pattern can be changed from an edge-to-face arrangement to that of a face-to-face motif. Before the work described herein, there were no reported studies of the supramolecular behavior of fused polycyclic aromatic compounds with partial peripheral fluorination, inducing the desired face-to-face behavior. This is the main focus of the thesis. Furthermore, by exploiting the interactions between the fluorinated and non-fluorinated faces of the molecule, columnar liquid crystalline behavior can be achieved through variations of the alkyl substituents on the molecule.

<p>The ability of gold(I) complexes to function as catalysts for myriad organic transformations has led to a dramatic increase in their utilization. Among the homogeneous reactions catalyzed by gold(I), carbon-carbon and carbon-heteroatom bond forming processes are of particular interest for the fields of organic synthesis and pharmaceutical development. Discussed herein are gold(I)-catalyzed methods for the intra- and intermolecular functionalization of alkenes, alkynes, and allenes with nitrogen- and oxygen-based nucleophiles leading to new C&#8210;X bonds (X = N, O).</p><p>Approximately 26 cationic gold &pi;-alkene complexes, containing either IPr [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] or P(t-Bu)2o-biphenyl ancillary ligands, were isolated or generated and six complexes were analyzed by X-ray crystallography. Spectroscopy, X-ray crystallography, and alkene binding studies are in accord with a gold&#8722;(&#960;-alkene) interaction dominated by &sigma;-donation from the alkene to gold. Kinetic analyses of degenerate isobutylene exchange in both the IPr and phosphine systems are consistent with associative pathways for isobutylene exchange involving cationic bis(alkene) intermediates.</p><p>Reaction of a 1:1 mixture of (L)AuCl [L = P(t-Bu)₂o-biphenyl or IPr] and AgSbF₆ with internal alkynes led to isolation of the corresponding cationic, two-coordinate gold &pi;-alkyne complexes in &#8805;90% yield. Equilibrium binding studies show that the binding affinities of alkynes to gold(I) are strongly affected by the electron density of the alkyne and to a lesser extent on the steric bulk of the alkyne. Treatment of a suspension of (IPr)AuCl and AgSbF₆ with terminal arylacetylenes led to the formation of thermally unstable gold &pi;-alkyne complexes of the form [(IPr)Au(eta<super>2</super>-HC&#8801;CAr)] SbF₆ in &#8805;86 ± 5% yield, which were characterized by spectroscopy without isolation. Warming these complexes to 0 °C led to C(sp)-H bond cleavage and formation of dinuclear gold(I) &sigma;,&pi;-acetylide complexes of the form {[(IPr)Au]₂(eta<super>1</super>,eta<super>2</super>-C&#8801;CAr)} SbF₆, three of which were isolated in 99% yield and one of which was characterized by X-ray crystallography.</p><p>A family of 7 cationic gold(I) &pi;-allene complexes were isolated and fully characterized in solution, and in three cases by X-ray crystallography. Degenerate intermolecular allene exchange kinetic studies for three of the allene complexes are in accord with a two-term rate law of the form rate = k1[complex] + k2[complex][allene] with with Gibb's free energy barriers of 17.4 - 18.8 kcal mol<super>-1</super> (1) and 15.2 - 17.6 kcal mol<super>-1</super> (2). Variable temperature NMR analysis of these complexes established facile intramolecular &#61552;-face exchange through &#61544;1-allene intermediates or transition states with barriers of 8.9 - 10.9 kcal mol<super>-1</super> for phosphine and 9.5 - 12.2 kcal mol<super>-1</super> for IPr complexes.</p><p>Mechanistic investigation of gold(I)-catalyzed intramolecular allene hydroalkoxylation established a mechanism involving rapid and reversible C-O bond formation followed by turnover-limiting protodeauration from a mono(gold) vinyl complex. This on-cycle pathway competes with catalyst aggregation and formation of an off-cycle bis(gold) vinyl complex.</p> / Dissertation