Carbon-carbon bond formation : from transition metal catalysis to base-promoted homolytic aromatic substitution

Cette thèse de doctorat porte sur la catalyse à partir de métaux de transition et sur la substitution homolytique aromatique favorisée par une base visant à former de nouvelles liaisons C–C, et à ainsi concevoir de nouvelles structures chimiques. Au cours des vingt dernières années, des nombreux efforts ont été réalisés afin de développer des méthodologies pour la fonctionnalisation de liens C–H, qui soient efficaces et sélectives, et ce à faible coût et en produisant le minimum de déchets. Le chapitre d'introduction donnera un aperçu de la fonctionnalisation directe de liens C–H sur des centres sp2 et sp3. Il sera également discuté dans cette partie de certains aspects de la chimie radicalaire reliés a ce sujet. Les travaux sur la fonctionnalisation d’imidazo[1,5-a]pyridines catalysée par des compleces de ruthénium seront présentés dans le chapitre 2. Malgré l'intérêt des imidazo[1,5-a]azines en chimie médicinale, ces composés n’ont reçu que peu d'attention dans le domaine de la fonctionnalisation de liens C–H. L'étendue de la réaction et l'influence des effets stériques et électroniques seront détaillés. Les cyclopropanes représentent les 10ème cycles carbonés les plus rencontrés dans les petites molécules d’intérêt pharmacologique. Ce sont aussi des intermédiaires de synthèse de choix pour la création de complexité chimique. Malgré de grands progrès dans le domaine de la fonctionnalisation de liens C(sp3)–H, l'étude des cyclopropanes comme substrats dans les transformations directes est relativement nouvelle. Le chapitre trois présentera l'arylation intramoléculaire directe de cyclopropanes. Cette réaction est réalisée en présence de palladium, en quantité catalytique, en combinaison avec des sels d’argent. Des études mécanistiques ont réfuté la formation d'un énolate de palladium et suggéreraient plutôt une étape de métallation - déprotonation concertée. En outre, les cycles de type benzoazepinone à sept chaînons ont été synthétisés par l'intermédiaire d'une séquence d'activation de cyclopropane/ouverture/cyclisation. Une arylation directe intermoléculaire des cyclopropanes a été réalisée en présence d'un auxiliaire de type picolinamide (Chapitre 4). Les deux derniers chapitres de ce mémoire de thèse décriront nos études sur la substitution homolytique aromatique favorisée par une base. Le mécanisme de la réaction de cyclisation intramoléculaire d'halogénures d'aryle, réalisée en présence de tert-butylate de potassium, a été élucidé et se produit via une voie radicalaire (Chapitre 5). La transformation, exempte de métaux de transition, ne nécessite que la présence d’une base et de pyridine comme solvant. Cette réaction radicalaire a été étendue à la cyclisation d'iodures d'alkyle non activés en présence d'un catalyseur à base de nickel et de bis(trimethylsilyl)amidure de sodium comme base (Chapitre 6). Des études de RMN DOSY ont démontré une association entre le catalyseur, la base et le matériel de départ.

Thumb-bangers : exploring the cultural bond between video games and heavy metal

« Heavy Metal Generations » is the fourth volume in the series of papers drawn from the 2012 Music, Metal and Politics international conference (http://www.inter-disciplinary.net/publishing/product/heavy-metal-generations/).

Studies on the fracture behaviour of polymer blends with special reference to PP/HDPE and PS/HIPS blends

Investigations on the fracture behaviour of polymer blends is the topic of this thesis. The blends selected are PP/HDPE and PS/HIPS. PP/HDPE blend is chosen due to its commercial importance and PS/HIPS blend is selected to study the transition from brittle fracture to ductile fracture.PP/HDPE blends were prepared at different compositions by melt blending at 180°C and fracture failure process was investigated by conducting notch sensitivity test and tensile test at different strain rates. The effects of two types of modifiers (particulate and elastomer) on the fracture behaviour and notch sensitivity of PP/HDPE blends were studied. The modifiers used are calcium carbonate, a hard particulate filler commonly used in plastics and Ethylene Propylene Diene Monomer (EPDM). They were added in 2%, 4% and 6% by weight of the blends.The study shows that the mechanical properties of PP/HDPE blends can be optimized by selecting proper blend compositions. The selected modifiers are found to alter and improve the fracture behaviour and notch sensitivity of the blends. Particulate fillers like calcium carbonate can be used for making the mechanical behaviour more stable at the various blend compositions. The resistance to notch sensitivity of the blends is found to be marginally lower in the presence of calcium carbonate. The elastomeric modifier EPDM produces a better stability of the mechanical behaviour. A low concentration of EPDM is sufficient to effect such a change. EPDM significantly improves the resistance to notch sensitivity of the blends. The study shows that judicious selection of modifiers can improve the fracture behaviour and notch sensitivity of PP/HDPE blends and help these materials to be used for critical applications.For investigating the transition in fracture behaviour and failure modes, PS/HIPS blends were selected. The blends were prepared by melt mixing followed by injection moulding to prepare the specimens for conducting tensile, impact and flexure tests. These tests were used to simulate the various conditions which promote failure.The tensile behaviour of unnotched and notched PS/HIPS blend samples were evaluated at slow speeds. Tensile strengths and moduli were found to increase at the higher testing speed for all the blend combinations whereas maximum strain at break was found to decrease. For a particular speed of testing, the tensile strength and modulus show only a very slight decrease as HIPS content is increased up to about 40%. However, there is a drastic decrease on increasing the HIPS content thereafter.The maximum strain at break shows only a very slight change up to about 40% HIPS content and thereafter shows a remarkable increase. The notched specimens also follow a comparable trend even though the notch sensitivity is seen high for PS rich blends containing up to 40% HIPS. The notch sensitivity marginally decreases with increase in HIPS content. At the same time, it is found to increase with the increase in strain rate. It is observed that blends containing more than 40% HIPS fail in ductile mode.The impact characteristics of PSIHIPS blends studied were impact strength, the energy absorbed by the test specimen and impact toughness. Remarkable increase in impact strength is observed as HIPS content in the blend exceeds 40%. The energy absorbed by the test specimens and the impact toughness also show a comparable trend.Flexural testing which helps to characterize the load bearing capacity was conducted on PS/HIPS blend samples at the two different testing speeds of 5mmlmin and 10 mm/min. The flexural strength increases with increase in testing speed for all the blend compositions. At both the speeds, remarkable reduction in flexural strength is observed as HIPS content in the blend exceeds 40%. The flexural strain and flexural energy absorbed by the specimens are found to increase with increase in HIPS content. At both the testing speeds, brittle fracture is observed for PS rich blends whereas HIPS rich blends show ductile mode of failure.Photoelastic investigations were conducted on PS/HIPS blend samples to analyze their failure modes. A plane polariscope with a broad source of light was utilized for the study. The coloured isochromatic fringes formed indicate the presence of residual stress concentration in the blend samples. The coverage made by the fringes on the test specimens varies with the blend composition and it shows a reducing trend with the increase in HIPS content. This indicates that the presence of residual stress is a contributing factor leading to brittle fracture in PS rich blends and this tendency gradually falls with increase in HIPS content and leads to their ductile mode of failure.

Studies in molecular mechanics using spectroscopic data exact force field and bond in homogeneity

This thesis deals with some studies in molecular mechanic using spectroscopic data. It includes an improvement in the parameter technique for the evaluation of exact force fields, the introduction of a new and simple algebraic method for the force field calculation and a study of asymmetric variation of bonding forces along a bond.

Palladium Catalyzed Carbon-Carbon/Carbonheteroatom Bond Formation Reactions Utilizing Pentafulvene Derived Bicyclic Hydrazines

The reactions involving fulvenes and its derivatives have received a great deal of attention over the years in synthetic organic chemistry. Functionalizations of fulvenes provide versatile and powerful approaches to various polycyclic systems and natural products. They serve as versatile intermediates in the construction of various ring systems through inter- as well as intramolecular cycloadditions. Compared to the rich literature on the cycloaddition reactions of pentafulvenes, much less attention has been paid to the synthetic utilization of their cycloadducts. Tactical manipulations on the chosen adduct offer the prospects for designing a variety of useful molecular skeletons. Addition of heterodienophiles to fulvenes offers an efficient strategy towards the synthesis of azabicyclic olefins. However, there have been no serious attempts to study the synthetic utility of these substrates. In this context and with the intention of utilizing pentafulvenes towards synthetically important molecules, author decided to explore the reactivity of pentafulvene derived azabicyclic olefins. Our attention was focused on the synthetic potential associated with the ring opening of fulvene derived bicyclic hydrazines under palladium catalysis. It was envisioned that the desymmetrization of these adducts using various soft nucleophiles will provide a novel access to synthetically and biologically important alkylidene cyclopentenes. The investigations along this line form the focal theme of this thesis entitled “PALLADIUM CATALYZED CARBONCARBON/ CARBON-HETEROATOM BOND FORMATION REACTIONS UTILIZING PENTAFULVENE DERIVED BICYCLIC HYDRAZINES

Behavior of geopolymer concrete exposed to elevated temperatures

The research in the area of geopolymer is gaining momentum during the past 20 years. Studies confirm that geopolymer concrete has good compressive strength, tensile strength, flexural strength, modulus of elasticity and durability. These properties are comparable with OPC concrete.There are many occasions where concrete is exposed to elevated temperatures like fire exposure from thermal processor, exposure from furnaces, nuclear exposure, etc.. In such cases, understanding of the behaviour of concrete and structural members exposed to elevated temperatures is vital. Even though many research reports are available about the behaviour of OPC concrete at elevated temperatures, there is limited information available about the behaviour of geopolymer concrete after exposure to elevated temperatures. A preliminary study was carried out for the selection of a mix proportion. The important variable considered in the present study include alkali/fly ash ratio, percentage of total aggregate content, fine aggregate to total aggregate ratio, molarity of sodium hydroxide, sodium silicate to sodium hydroxide ratio, curing temperature and curing period. Influence of different variables on engineering properties of geopolymer concrete was investigated. The study on interface shear strength of reinforced and unreinforced geopolymer concrete as well as OPC concrete was also carried out. Engineering properties of fly ash based geopolymer concrete after exposure to elevated temperatures (ambient to 800 °C) were studied and the corresponding results were compared with those of conventional concrete. Scanning Electron Microscope analysis, Fourier Transform Infrared analysis, X-ray powder Diffractometer analysis and Thermogravimetric analysis of geopolymer mortar or paste at ambient temperature and after exposure to elevated temperature were also carried out in the present research work. Experimental study was conducted on geopolymer concrete beams after exposure to elevated temperatures (ambient to 800 °C). Load deflection characteristics, ductility and moment-curvature behaviour of the geopolymer concrete beams after exposure to elevated temperatures were investigated. Based on the present study, major conclusions derived could be summarized as follows. There is a definite proportion for various ingredients to achieve maximum strength properties. Geopolymer concrete with total aggregate content of 70% by volume, ratio of fine aggregate to total aggregate of 0.35, NaOH molarity 10, Na2SiO3/NaOH ratio of 2.5 and alkali to fly ash ratio of 0.55 gave maximum compressive strength in the present study. An early strength development in geopolymer concrete could be achieved by the proper selection of curing temperature and the period of curing. With 24 hours of curing at 100 °C, 96.4% of the 28th day cube compressive strength could be achieved in 7 days in the present study. The interface shear strength of geopolymer concrete is lower to that of OPC concrete. Compared to OPC concrete, a reduction in the interface shear strength by 33% and 29% was observed for unreinforced and reinforced geopolymer specimens respectively. The interface shear strength of geopolymer concrete is lower than ordinary Portland cement concrete. The interface shear strength of geopolymer concrete can be approximately estimated as 50% of the value obtained based on the available equations for the calculation of interface shear strength of ordinary portland cement concrete (method used in Mattock and ACI). Fly ash based geopolymer concrete undergoes a high rate of strength loss (compressive strength, tensile strength and modulus of elasticity) during its early heating period (up to 200 °C) compared to OPC concrete. At a temperature exposure beyond 600 °C, the unreacted crystalline materials in geopolymer concrete get transformed into amorphous state and undergo polymerization. As a result, there is no further strength loss (compressive strength, tensile strength and modulus of elasticity) in geopolymer concrete, whereas, OPC concrete continues to lose its strength properties at a faster rate beyond a temperature exposure of 600 °C. At present no equation is available to predict the strength properties of geopolymer concrete after exposure to elevated temperatures. Based on the study carried out, new equations have been proposed to predict the residual strengths (cube compressive strength, split tensile strength and modulus of elasticity) of geopolymer concrete after exposure to elevated temperatures (upto 800 °C). These equations could be used for material modelling until better refined equations are available. Compared to OPC concrete, geopolymer concrete shows better resistance against surface cracking when exposed to elevated temperatures. In the present study, while OPC concrete started developing cracks at 400 °C, geopolymer concrete did not show any visible cracks up to 600 °C and developed only minor cracks at an exposure temperatureof 800 °C. Geopolymer concrete beams develop crack at an early load stages if they are exposed to elevated temperatures. Even though the material strength of the geopolymer concrete does not decrease beyond 600 °C, the flexural strength of corresponding beam reduces rapidly after 600 °C temperature exposure, primarily due to the rapid loss of the strength of steel. With increase in temperature, the curvature at yield point of geopolymer concrete beam increases and thereby the ductility reduces. In the present study, compared to the ductility at ambient temperature, the ductility of geopolymer concrete beams reduces by 63.8% at 800 °C temperature exposure. Appropriate equations have been proposed to predict the service load crack width of geopolymer concrete beam exposed to elevated temperatures. These equations could be used to limit the service load on geopolymer concrete beams exposed to elevated temperatures (up to 800 °C) for a predefined crack width (between 0.1mm and 0.3 mm) or vice versa. The moment-curvature relationship of geopolymer concrete beams at ambient temperature is similar to that of RCC beams and this could be predicted using strain compatibility approach Once exposed to an elevated temperature, the strain compatibility approach underestimates the curvature of geopolymer concrete beams between the first cracking and yielding point.

Theory for the change of bond character in divalent-metal clusters

To determine the size dependence of the bonding in divalent-metal clusters we use a many-electron Hamiltonian describing the interplay between van der Waals (vdW) and covalent interactions. Using a saddle-point slave-boson method and taking into account the size-dependent screening of charge fluctuations, we obtain for Hg_n a sharp transition from vdW to covalent bonding for increasing n. We show also, by solving the model Hamiltonian exactly, that for divalent metals vdW and covalent bonding coexist already in the dimers.

Electronic origin of bond softening and hardening in femtosecond-laser-excited magnesium

Many ultrafast structural phenomena in solids at high fluences are related to the hardening or softening of particular lattice vibrations at lower fluences. In this paper we relate femtosecond-laser-induced phonon frequency changes to changes in the electronic density of states, which need to be evaluated only in the electronic ground state, following phonon displacement patterns. We illustrate this relationship for a particular lattice vibration of magnesium, for which we—surprisingly—find that there is both softening and hardening as a function of the femtosecond-laser fluence. Using our theory, we explain these behaviours as arising from Van Hove singularities: We show that at low excitation densities Van Hove singularities near the Fermi level dominate the change of the phonon frequency while at higher excitations Van Hove singularities that are further away in energy also become important. We expect that our theory can as well shed light on the effects of laser excitation of other materials.

The relationships of character strengths with coping, work-related stress, and job satisfaction

Personality traits have often been highlighted to relate to how people cope with stressful events. The present paper focuses on character strengths as positive personality traits and examines two basic assumptions that were derived from a core characteristic of character strengths (i.e., to determine how individuals deal with adversities): (1) character strengths correlate with coping and (2) buffer the effects of work-related stress on job satisfaction. Two different samples (i.e., a mixed sample representing various occupations [N = 214] and a nurses sample [N = 175]) filled in measures for character strengths, coping, work-related stress, and job satisfaction. As expected, intellectual, emotional, and interpersonal strengths were related to coping. Interpersonal strengths played a greater role for coping among nurses, as interactions with others are an essential part of their workday. Furthermore, intellectual strengths partially mediated the negative effect of work-related stress on job satisfaction. These findings open a new field for research on the role of personality in coping with work-related stress. Character strengths are trainable personal characteristics, and therefore valuable resources to improve coping with work-related stress and to decrease the negative effects of stress. Further research is needed to investigate this assumed causality.

Análisis del significado de conflicto en un grupo de jóvenes de la Universidad del Rosario desde el Modelo Relacional Simbólico

Esta investigación se propuso definir y reflexionar acerca de las concepciones de conflicto, reportadas por un grupo de jóvenes de la Universidad del Rosario, identificando si se consideraba el vínculo y las categorías simbólicas del Modelo Relacional Simbólico: confianza, justicia y esperanza. Se realizaron entrevistas semiestructuradas, que se analizaron en su contenido. Se logró establecer que la concepción predominante acerca del conflicto fue la de algo que no debe suceder o debe evitarse, entendido en general como una confrontación o un choque. Ninguno consideró el vínculo como un elemento fundamental o vital del conflicto. Se pudo deducir que el conflicto se da en las relaciones entre personas, pero la importancia del vínculo en términos de encuentro de generaciones, estirpes y géneros, como un espacio de confianza, esperanza y justicia en las que se entregan dones y se tienen deudas; no está presente de ninguna forma en las definiciones de conflicto. Estos aspectos muestran la necesidad de acoger los fundamentos vinculares y simbólicos del modelo, como riquezas y fortalezas que necesitan ser introducidas en la cotidianidad de la población Colombiana, en la construcción de una cultura de la paz. Esto, a través de la educación a todo nivel y en particular a corto plazo; con los estudiantes de primeros semestres universitarios, por el papel que como profesionales tendrán de líderes sociales, empresariales, espirituales, políticos y laborales; y porque aún se encuentran en una etapa propicia para la formación integral que estimule el fortalecimiento del vínculo como un eje vital de las relaciones y en el que sus categorías simbólicas (esperanza, justicia y confianza) se vuelvan parte conciente en las relaciones personales, familiares y sociales. Igualmente se hace indispensable transformar la visión de conflicto; de forma que deje de ser negativo, no deseable y se convierta en parte de la vida y en una oportunidad para crecer, conocer, generar y regenerar vínculos. Finalmente se propone la creación de una línea de investigación que extienda el estudio a otras poblaciones de jóvenes de distinto nivel socioeconómico y cultural, incluidos los afectados directa e indirectamente por la violencia en Colombia.

Calculating Team Character Strengths

Individuals need to have completed the VIA Character Strengths Survey prior to this activity as they will need to know their top 5 'signature' Character Strengths. This Excel Spreadsheet can be used to look at the Team Culture and to align team members' top Strengths with 7 key Team Functions

Reaching and teaching the child with autism spectrum disorder : using learning preferences and strengths.

Manual que ofrece un enfoque positivo a la comprensión y la educación de los niños con autismo. Ofrece una mayor comprensión de la perspectiva y el comportamiento de un niño con autismo y explora cómo pueden utilizarse sus preferencias de aprendizaje, fortalezas e intereses para facilitar el aprendizaje y aumentar la motivación. La autora ha utilizado una mezcla de teorías de la personalidad, inteligencias múltiples y aprendizaje para crear un método de trabajo, Aprendizaje Preferencias y Fortalezas (LPS), para el desarrollo de habilidades de aprendizaje para la vida independiente en niños con autismo entre dos y doce años. Describe los principios básicos, preferencias de aprendizaje y los puntos fuertes típicos de los niños con autismo y ofrece una estructura de programa detallado, pero flexible, basada en estos conceptos. Fácil de seguir, se describen en cada capítulo actividades y orientaciones junto con ejemplos e ilustraciones.

Quantification of the bond-angle dispersion by Raman spectroscopy and the strain energy of amorphous silicon

A thorough critical analysis of the theoretical relationships between the bond-angle dispersion in a-Si, Δθ, and the width of the transverse optical Raman peak, Γ, is presented. It is shown that the discrepancies between them are drastically reduced when unified definitions for Δθ and Γ are used. This reduced dispersion in the predicted values of Δθ together with the broad agreement with the scarce direct determinations of Δθ is then used to analyze the strain energy in partially relaxed pure a-Si. It is concluded that defect annihilation does not contribute appreciably to the reduction of the a-Si energy during structural relaxation. In contrast, it can account for half of the crystallization energy, which can be as low as 7 kJ/mol in defect-free a-Si