Late transition metal complexes of silver(I), rhodium(I), ruthenium(II), palladium(II) and platinum(II) containing a nitrile-functionalized N-heterocyclic carbene ligand (C-CN) were prepared. The nitrile group on the C–CN ligand was shown to undergo hydrolysis under basic conditions, leading to a silver(I) carbene complex with a primary-amido functional group, and a trimetallic complex of palladium(II) with a partially hydrolyzed C–N–N–C donor ligand. The reduction of a nitrile-functionalized imidazolium salt in the presence of nickel(II) chloride under mild conditions yielded an axially chiral square-planar nickel(II) complex containing a unique primary-amino functionalized N-heterocyclic carbene ligand (C-NH2). A transmetalation reaction moved this chelating C–NH2 ligand from nickel(II) to ruthenium(II), osmium(II), and iridium(III), yielding important catalysts for the hydrogenation of polar double bonds. The ruthenium(II) complex, [Ru(p-cymene)(C–NH2)Cl]PF6 catalyzed the transfer and H2-hydrogenation of ketones. The bifunctional hydride complex, [Ru(p-cymene)(C–NH2)H]PF6, which contains a Ru–H/N–H couple showed no activity under catalytic conditions unless when activated by a base. The outer-sphere mechanism involving bifunctional catalysis of ketone reduction is disfavored according to experimental and theoretical studies and an inner-sphere mechanism is proposed involving the decoordination of the amine donor from the C–NH2 ligand. The ruthenium(II) complex [RuCp*(C–NH2)py]PF6 showed higher activity than the iridium(III) complex [IrCp*(C–NH2)Cl]PF6 in the hydrogenation of ketones. This ruthenium(II) complex also catalyzes the hydrogenation of an aromatic ester, a ketimine, and the hydrogenolysis of styrene oxide. We proposed an alcohol-assisted outer sphere bifunctional mechanism for both systems based on experimental findings and theoretical calculations. The cationic iridium(III) hydride complex, [IrCp*(C–NH2)H]PF6 , was prepared and this failed to react with a ketone in the absence of base. The crucial role of the alkoxide base was demonstrated in the activation of this hydride complex in catalysis. Calculations support the proposal that the base deprotonates the amine group of this hydride complex and triggers the migration of the hydride to the η5-Cp* ring producing a neutral iridium(I) amido complex. This system contains an active Ir–H/N–H couple required for the outer sphere hydrogenation of ketones in the bifunctional mechanism.

Late transition metal complexes of silver(I), rhodium(I), ruthenium(II), palladium(II) and platinum(II) containing a nitrile-functionalized N-heterocyclic carbene ligand (C-CN) were prepared. The nitrile group on the C–CN ligand was shown to undergo hydrolysis under basic conditions, leading to a silver(I) carbene complex with a primary-amido functional group, and a trimetallic complex of palladium(II) with a partially hydrolyzed C–N–N–C donor ligand. The reduction of a nitrile-functionalized imidazolium salt in the presence of nickel(II) chloride under mild conditions yielded an axially chiral square-planar nickel(II) complex containing a unique primary-amino functionalized N-heterocyclic carbene ligand (C-NH2). A transmetalation reaction moved this chelating C–NH2 ligand from nickel(II) to ruthenium(II), osmium(II), and iridium(III), yielding important catalysts for the hydrogenation of polar double bonds. The ruthenium(II) complex, [Ru(p-cymene)(C–NH2)Cl]PF6 catalyzed the transfer and H2-hydrogenation of ketones. The bifunctional hydride complex, [Ru(p-cymene)(C–NH2)H]PF6, which contains a Ru–H/N–H couple showed no activity under catalytic conditions unless when activated by a base. The outer-sphere mechanism involving bifunctional catalysis of ketone reduction is disfavored according to experimental and theoretical studies and an inner-sphere mechanism is proposed involving the decoordination of the amine donor from the C–NH2 ligand. The ruthenium(II) complex [RuCp*(C–NH2)py]PF6 showed higher activity than the iridium(III) complex [IrCp*(C–NH2)Cl]PF6 in the hydrogenation of ketones. This ruthenium(II) complex also catalyzes the hydrogenation of an aromatic ester, a ketimine, and the hydrogenolysis of styrene oxide. We proposed an alcohol-assisted outer sphere bifunctional mechanism for both systems based on experimental findings and theoretical calculations. The cationic iridium(III) hydride complex, [IrCp*(C–NH2)H]PF6 , was prepared and this failed to react with a ketone in the absence of base. The crucial role of the alkoxide base was demonstrated in the activation of this hydride complex in catalysis. Calculations support the proposal that the base deprotonates the amine group of this hydride complex and triggers the migration of the hydride to the η5-Cp* ring producing a neutral iridium(I) amido complex. This system contains an active Ir–H/N–H couple required for the outer sphere hydrogenation of ketones in the bifunctional mechanism.

This thesis examines the elegant theory of polar and Legendre duality, and its potential use in convex geometry and geometric analysis. It derives a theorem of polar - Legendre duality for all convex bodies, which is captured in a commutative diagram. A geometric flow on a convex body induces a distortion on its polar dual. In general these distortions are not flows defined by local curvature, but in two dimensions they do have similarities to the inverse flows on the original convex bodies. These ideas can be extended to higher dimensions. Polar - Legendre duality can also be used to examine Mahler's Conjecture in convex geometry. The theory presents new insight on the resolved two-dimensional problem, and presents some ideas on new approaches to the still open three dimensional problem.

This exegesis interrogates the mental illness Pure Erotomania, the rare delusional disorder which presents with the sufferer having the delusional (and therefore unshakeable) belief that the person they objectify is in love with them. My play Yellow Roses in Fortitude Valley is about one woman's emotional journey as she is relentlessly stalked by a Pure Erotomanic male. It is a fascinating mental illness, which includes all the 'box office type' features, which make it an exciting and frightening subject to write a dramatic work about. It is confusing, illusory, surreal and frightening, but best of all for the writer and audience it is a real human condition. Yellow Roses in Fortitude Valley is written in a style that truthfully represents and portrays the journey and struggle for both the victim and the sufferer. The research undertaken for both the play and exegesis was a hybrid of many overlapping disciplines involved in the current discourse. As a recently diagnosed and recognized disorder, it is still new territory for professionals in the field and for audience members. I believe this makes it an opportune time for an academically researched creative project to enter into current discourse. Previous creative works on this topic, some of which I have interrogated, have approached the issue of stalking as a predator/victim scenario, an unrequited love or a domestic violence situation. I wished to portray the stalking as a mental illness in the form of the psychiatric disorder Erotomania, my approach undertaking to explain victim impact and the prolonged and chronic course of Erotomanic stalking. I also wished to illustrate the underlying themes which I uncovered during my research, being; female victims of sex crimes; dominant patriarchal ideology; and the current interventions in stalking by the legal and mental health systems.

The Quasi-Biennial Oscillation (QBO) is the strongest phenomena influencing the stratopheric (~15-50 km height) circulation over the equator. QBO has two phases of downward propagating easterly and westerly winds, which has a total period of approximately 28 months and the phase is defined by the wind direction between the airpressure 25-50 hPa, which is roughly at a height of 30 km. QBO is induced by atmospheric gravity waves originating from the troposphere (~0-15 km height) and are generated by a plethora of sources, such as tropical convection and wind shear. The winds propagate downward at about 1 km per month through the stratosphere until reaching the tropopause (~15 km height) where they dissipate. The wind speed is at its maximum in the middle of the phase, where the wind shear is at its lowest, and the easterly winds can grow up to 30 m/s whilst the westerly winds reach roughly 15 m/s. Although the QBO is an equatorial phenomena it has a poleward component radiating its signal from the tropics to the higher latitudes where it affects other circulations such as the stratospheric polar vortex on the northern hemisphere (NH). The polar vortex consists of westerly winds around the polar region and is a major influence on the winter climate on the NH and thereby allows the QBO to indirectly affect the tropospheric climate through it. The easterly QBO disturbs and weakens the polar vortex, which results in warm subtropical air penetrating the vortex and warming the Arctic region whereas the polar air is released southward creating a colder winter on the NH. The westerly QBO on the other hand enhances the polar vortex and contains the cool polar air over the Arctic, which results in a milder winter. The correlation between QBO and El Niño Southern Oscillation (ENSO) as well as the tropical cyclones (TC) has either changed (ENSO) or completely disappeared (TC). The ENSO-QBO correlation depends on which phase of ENSO coincide with which phase of QBO, where El Niño coinciding with easterly QBO and La Niña coinciding with westerly QBO results in wind anomalies in the NH stratosphere. If the opposite combination takes place the wind anomalies will instead be situated in the subtropical troposphere, displacing the subtropical jet poleward. To what extent these stratospheric winds exert their influence is to some degree still uncertain, but that they have an effect on the tropospheric climate is unbeknownst to no one. / Cirkulationen i den ekvatoriella stratosfären (ca 15-50 km höjd) domineras av Quasi-Biennial Oscillation (QBO), ett zonalt (parallellt ekvatorn) vindfenomen med två faser bestående av östliga respektive västliga vindar och en period på ca 28 månader. Fasen definieras mellan lufttrycken 25-50 hPa, vilket representerar en höjd på ca 30 km. Drivkraften bakom QBO är ett brett spektrum av atmosfäriska gravitationsvågor som skapas genom bland annat den tropiska konvektionen, vindskjuvning och frontsystem. Vindarna propagerar vertikalt nedåt genom stratosfären med ungefär 1 km per månad tills de når tropopausen (ca 15 km) där vindarna försvagas kraftigt till ett zonalt medelvärde på 0 m/s. Vindhastigheten under östlig QBO uppgår i ca 30 m/s medan västlig QBO uppgår i ca 15 m/s, och är maximal i höga stratosfären samt i mitten av faserna där vindskjuvningen är minimal. QBO sprider sig meridionalt (nord-syd) från tropikerna till högre breddgrader genom stratosfären där andra fenomen som den stratosfäriska polarvirveln kan påverkas på norra halvklotet (NH). Polarvirveln består av västliga vindar i stratosfären runt polarregionen och är en stor influens på vinterklimatet i framförallt Europa och Nordamerika. Genom polarvirveln kan QBO indirekt påverka klimatet i troposfären (ca 0-15 km), där den östliga fasen av QBO försvagar medan den västliga fasen av QBO förstärker polarvirveln. En försvagad polarvirvel innebär en varmare medeltemperatur på Arktis och att kallare polarluft söker sig söderut och orsakar kalla vintertemperaturer. Troposfäriska klimatfenomen som El Niño Southern Oscillation (ENSO) och tropiska cykloner (TC) har uppvisat ett samband till QBO, men sedan förändrats (ENSO) eller helt försvunnit (TC). ENSO-QBO korrelationen förändras beroende på vilken fas QBO respektive ENSO är i relativt varandra. Då El Niño sammanfaller med östliga QBO samt La Niña sammanfaller med västliga QBO uppstår vindanomalier vid höga latituder i NH:s stratosfär, medan vid omvända sambandet förflyttar sig vindanomalierna till subtropikerna i troposfären och kan där förskjuta den subtropiska jetströmmen norrut. Att de stratosfäriska vindarna påverkar troposfären är känt, men hur och till vilken grad är ännu inte uppenbart. På grund av den korta tidsperiod med kontinuerliga och tillförlitliga vindmätningar i stratosfären uppkommer flera hypotetiska effekter av QBO och dess påverkan på klimatet i troposfären.

Rotating blades are considered to be the one of the most common cause of failures in rotating machinery. Blade failure modes normally occur as a result of cracks due to unexpected operating conditions, which are normally caused by accidents of foreign objects damage, high cycle fatigue, blade rubbing, blade root looseness, and degradation from erosion and corrosion. Thus, detection of blade faults has an important role in reducing blade related failures and allowing repairs to be scheduled for the machinery. This in turn will lead to reduction in maintenance costs and thus raise productivity and safety aspects of operation. To maintain vital components of rotating machines, such as blades, shafts, bearings and gear boxes, at optimal levels, detection of failures in such components is important, because this will prevent any serious damage that could affect performance. This research study involves laboratory tests on a small rig with a bladed disc rotor that applied vibration measurements and analysis for blade fault detection. Three measurements: shaft torsional vibration, on-bearing vibration (OBV) and on-casing vibration (OCV), are used. A small test rig of a single stage bladed disc holding 8-blades was designed and manufactured, to carry out this research study to assess the usefulness and capability of each vibration technique in detection of incipient defects within machine blades. A series of tests was conducted on a test rig for three different cases of blade health conditions: (a) healthy blade(s) with mistuned effects, (b) blade root looseness and (c) cracks in a blade on two different blade sizes (long and short blades) in order to discover changes in blades' dynamic behaviour during the machine running-up operation. The data were collected using the three measurements during machine run-up and then recorded. The measured vibration data were analysed by computing the blades' resonance at different engine orders (EOs) related to the blade(s) resonance frequencies and their higher harmonics, to understand the blade(s) dynamics behaviour for the cases of healthy and faulty blade(s). Data have been further processed using a polar plot presentation method which provides clear results that can be used for monitoring blade integrity. To validate the obtained experimental results, a simplified mathematical model was also developed. Finally, a comparative study between three methods was undertaken to understand the relative advantages and limitations in the blade heath monitoring.

Four continuous high-resolution peat records for the Holocene have been reconstructed across a ~300km transect from Shebster in Caithness to Yell in the Shetland Isles. These records describe the nature and extent of North Atlantic climate changes inferred from indicators of storminess and minerogenic aeolian dust, and are supported by radiogenic isotope analysis, tephrochronology and radiocarbon dating. The environmental changes at all four sites displays a significant degree of synchrony in response to changes in the position of the polar front jet (PFJ) stream and the phase of the North Atlantic Oscillation (NAO). Bromine concentrations in the peat, derived from sea spray, are used to reconstruct storm frequency and storm intensity, and mire surface wetness is used as an indicator of longer-term climate shifts. The results suggest a strong link between positive phases of the NAO and storminess. Subtle differences between the bromine concentrations and the mire surface wetness suggest that high intensity but perhaps less frequent periods of storminess are not necessarily associated with a wetter climate. Atmospheric minerogenic dust concentrations are used to reconstruct large-scale climate changes across the wider North Atlantic region. The results suggest a sympathy between dust activity and periods of glacial advance and a negative index of the NAO. Radiogenic isotope analysis suggests that the smallest particles may originate from Iceland.

L'intensification de l'effet de serre due à l'augmentation des concentrations de CO 2 dans l'atmosphère pourrait être plus élevée si ce n'est du rôle important de l'océan en tant que puits pour le CO 2 atmosphérique. Malheureusement, une conséquence de la capacité de l'océan à tamponner le CO 2 est l'acidification des eaux de surface des océans. L'océan Austral est particulièrement vulnérable à ces conséquences en raison de ses basses températures et de sa productivité primaire saisonnière élevée. La présente thèse de doctorat a comme objectif d’analyser le système des carbonates, en particulier l'état de l’acidification des océans, dans le détroit de Gerlache et dans la zone polaire de la région de la Terre Adélie. Ces deux régions présentent des hydrodynamiques différents et, par conséquent, devraient présenter des différences dans la variabilité de leur système carbonaté. À partir des données du programme brésilien NAUTILUS et du programme français MINERVE, la dynamique du système des carbonates a été évaluée dans ces régions de 2015 à 2017. Les résultats sont présentés sous la forme d'articles scientifiques qui ont été assemblés pour structurer cette thèse. Le détroit de Gerlache présentait les plus grandes variations spatiales des propriétés du système des carbonates avec des conditions potentiellement acides durant l'été austral. En comparaison, la zone polaire de Terre Adélie présente des variations interannuelles et spatiales plus importantes associées aux zones frontales. En raison de ses conditions géographiques et hydrodynamiques, le détroit de Gerlache est actuellement plus vulnérable à l'acidification des océans que la région de la Terre Adélie. / The intensification of the greenhouse effect due to increasing atmospheric CO 2 concentrations could be higher if not for the ocean’s important role as a sink for atmospheric CO 2 . A consequence of the ocean’s capacity for buffering CO 2 is the ocean acidification of sea surface waters. The Southern Ocean is particularly vulnerable to these consequences due to its low temperatures and high seasonal primary productivity. The present Ph.D. thesis focus on the analysis of the carbonate system, particularly the ocean acidification state, in the Gerlache Strait and the polar zone off the Adelie Land region. These two regions present different hydrodynamics and, consequently, are expected to present differences in their carbonate system variability. Using data sets from the Brazilian NAUTILUS programme and the French MINERVE programme, the carbonate system dynamic was assessed in these regions from 2015 to 2017. The results are presented as scientific articles, which were assembled to structure this thesis. The Gerlache Strait showed the largest spatial variations of carbonate system properties with potentially acidic conditions during austral summer. In comparison, the polar zone off Adelie Land larger inter-annual and spatial variations associated with frontal zones. Due to its geographical and hydrodynamic conditions, the Gerlache Strait is currently more vulnerable to ocean acidification than the off Adelie Landregion.

No description available.

L'utilisation de systèmes moléculaires individuels pouvant jouer le rôle de composants avec des fonctions électroniques ou logiques requiert des interfaces parfaitement contrôlées. Plus précisément, le support sur lequel ces systèmes sont déposés et les électrodes métalliques qui permettent de contacter une molécule individuelle, sont des interfaces qui nécessitent un soin d'élaboration particulier. La croissance d'îlots bidimensionnels (2d) de métaux sur un isolant monocristallin permet de générer des nano-plots 2d pouvant servir de réservoirs d'électrons en minimisant les courants de fuite en surface. Ainsi, il apparaît capital de bien comprendre les modes de croissance des systèmes métal/isolant qui sont à l'heure actuelle mal connus. Ce travail de thèse s'attache à décrire et à expliquer la croissance de différents métaux sur la surface de l'AlN(0001) polaire, qui est un composé nitrure à grand gap, par des calculs basés sur la théorie de la fonctionnelle de la densité (DFT).Dans un premier temps, une description approfondie des différentes surfaces du nitrure d'aluminium est présentée. Des calculs DFT ont permis de rationaliser les reconstructions en fonction des conditions expérimentales. La reconstruction (2 x 2)-Nad est discutée, puisqu'elle a été observée en microscopie à force atomique. Dans un deuxième temps, le cas du dépôt d'atomes d'or est abordé en connexion avec des résultats expérimentaux. Les calculs DFT donnent un aperçu des mécanismes qui conduisent à la stabilisation d'îlots 2d sur l'AlN. L'adsorption d'or s'accompagne, d'une part, d'un transfert de charge vertical provenant du substrat d'AlN, ce qui satisfait au critère de stabilité électrostatique pour un matériau polaire et, deuxièmement, par des transferts de charges horizontaux reliés aux propriétés acido-basiques locales de la reconstruction (2 x 2)-Nad. Enfin, des calculs effectués sur deux autres métaux, le magnésium et l'argent, sont exposés. Ces résultats ouvrent la voie à de nouvelles stratégies utilisant des substrats polaires pour développer des monocouches métalliques sur des substrats isolants. / The use of individual molecular systems that can act as components with electronic or logical functions requires perfectly controlled interfaces. More precisely, the support on which these systems are deposited and the metal electrodes that allow to contact an individual molecule, are interfaces that require special care in preparation. The growth of two-dimensional (2d) islands of metals on a monocrystalline insulator allows to generate 2d nano-pads that can be used as electron reservoirs by minimizing surface leakage currents. Thus, it is essential to understand the growth modes of metal/insulating systems which are at present poorly known. This work aims at describing and explaining the growth of different metals on the surface of the polar AlN (0001), which is a large gap nitride compound, by calculations based on density functional theory (DFT). In a first step, a detailed description of the various surfaces of the aluminum nitride is presented. DFT calculations permit to rationalize the reconstructions according to the experimental conditions. The (2 x 2)-Nad reconstruction is discussed, since it was observed by atomic force microscopy. In a second step, the case of the deposit of gold atoms is tackled in connection with experimental results. DFT calculations give an overview of the mechanisms that lead to the stabilization of 2d islands on AlN. The adsorption of gold is accompanied, on the one hand, by a vertical charge transfer from the AlN substrate, which satisfies the electrostatic stability criterion for a polar material and, on the other hand, by horizontal charge transfers related to the local acid-base properties of the (2 x 2)-Nad reconstruction. Finally, calculations made on two other metals, magnesium and silver, are exposed. These results open the way to new strategies using polar substrates to develop metallic monolayers on insulating substrates.