The main focus of this thesis is the topic of spin doctoring. We understand the term of spin doctoring as a one-sided manipulative form of communication whose aim is to influence public opinion and attitudes. The thesis deals with both historic concepts and present day definitions of spin. Based on academic work, this text examines the phenomenon of spin doctoring in relation to political communication, public relations, propaganda, corporate spin and journalistic professions. We elaborate particular techniques and methods of spin on the background of important cases related to spin doctoring. These specific cases refer to anglo-american countries. The field of interest of political communication, the relation of politics and media and their impact on democratic order of society is examined from the perspective of pluralistic pessimists and neo- liberal optimists. The position of journalists in the context of their cooperation with the spin doctors is also taken into account. The research part of this work deals with the spin doctoring in the case of "Radar". The aim of the research is to find out whether or not manipulative techniques were employed in order to gain consent and support of the public in the case of building an American radar base in the Czech territory. Quantitative research methods...

O presente trabalho descreve a investigação de funcionais de densidade para os cálculos das constantes escalares de acoplamento indireto spin-spin para diferentes tipos de átomos. 26 DFTs são inicialmente avaliados para um conjunto de calibração contendo constantes de acoplamento indireto spin-spin das moléculas HF, CO, H2O, NH3, PH3, PF3, BHF2, BF3, F2O, CH4, C2H2, C2H4 e C2H6. As estratégias utilizadas envolvem principalmente o ajuste da porcentagem de troca orbital Hartree-Fock (EXHF), a fim de melhorar a precisão. Estudos anteriores sugeriram que a utilização de uma certa porcentagem de troca exata contribui para obter resultados mais precisos para as constantes de acoplamento. Do total, BHandH, B1B95, a família B97 e a família ωB97 forneceram bons resultados para o conjunto de calibração. Em geral, DFTs híbridos contendo entre 30% e 50% de EXHF em sua composição apresentam valores mais precisos para as constantes de acoplamento. Os funcionais modificados B1B95 40% EXHF, BHandH 40% EXHF e B972B95 60% EXHF apresentam ótima precisão para rotinas de otimização de geometria e cálculo da constante de acoplamento. Para funcionais corrigidos no longo alcance, a porcentagem EXHF não é bem definida, mas pode ser ajustada em termos de três parâmetros. Uma versão de ωB97XD com γ incrementado para 0,35 tem ótima precisão, assim como umaversão de ωB97X com α incrementado para 0,2. Versões corrigidas no longo alcance de B1B95 e BHandH fornecem excelentes precisões com α =0,4, α + β =1,0 e γ ajustado ao funcional. Os funcionais de longo alcance e o B972B95 60% EXHF desafiam os níveis de teoria SOPPA(CCSD) e SOPPA(CC2), que apresentam boa precisão independente do tipo de núcleo envolvido no acoplamento. O termo do contato de Fermi está principalmente associado às diferenças nos resultados para as constantes de acoplamento calculadas entre os métodos. Segundo o teorema de Janak, os funcionais de longo alcance estão mais próximos do comportamento exato de um funcional; o aumento da troca exata em DFTs híbridos leva a um aumento da localização eletrônica, levando a concavidades menores. A utilização de um conjunto teste com mais tipos de acoplamento reforça a ótima precisão obtida com B1B95 40% EXHF, BHandH 40% EXHF e suas versões de longo alcance. / This work seeks to describe the investigation of density functionals for calculating indirect spin-spin scalar coupling constants for different types of atoms. 26 DFTs are initially evaluated for a calibration set containing HF, CO, H2O, NH3, PH3, PF3, BHF2, BF3, F2O, CH4, C2H2, C2H4 and C2H6 indirect spin-spin coupling constants. The strategies used mainly involve adjusting the percentage of Hartree-Fock orbital exchange (EXHF) in order to increase accuracy. Previous studies have suggested that the use of a certain percentage of exact exchange contributes to obtain more accurate results for coupling constants. Overall, BHandH, B1B95, B97 family and ωB97 family have provided good results for the calibration set. In general, hybrid DFTs containing between 30% and 50% EXHF in their composition show more accurate values for the coupling constants. The modified functionals B1B95 40% EXHF, BHandH 40% EXHF and B972B95 60% EXHF have optimal accuracy for geometry optimization and coupling constant calculation routines. For long-range corrected functionals, EXHF percentage is not well defined but can be adjusted in terms of three parameters. A version of ωB97XD with γ increased to 0.35 has great accuracy, as well as a version of ωB97X with α increased to 0.2. Long-range corrected versions of B1B95 and BHandH provided excellent accuracies with α =0.4, α + β =1.0 and γ adjusted to the functional. Long-range functionals and B972B95 60% EXHF challenge SOPPA(CCSD) and SOPPA(CC2) levels of theory, which have good accuracy regardless of the core type involved in the coupling. Fermi-contact term is mainly associated with the differences from results of calculated coupling constants between methods. According to Janaks theorem, long-range functionals are closest to the exact behavior of a functional; increasing exact exchange in hybrid DFTs leads to an increased electronic localization, leading to lower concavities. Using a test set with more coupling types reinforces the optimum accuracy obtained with B1B95 40% EXHF, BHandH 40% EXHF and their long-range versions.

Tato práce popisuje historicky první multi-frekvenční rapid-scan EPR. Při zavedení mikrovlnného záření z oblasti 200 GHz a následnou sinusovou modulací bylo dosaženo rychlostí změn frekvence až 61 500 THz/s a zkreslení spekter, známé jako ”wiggles”, bylo pozorováno u obou studovaných vzorků organických radikálů – BDPA v polystyrenové matici a LiPc. Tato práce představuje flexibilní metodu provádění rapid-scan EPR experimentů za použití napětím ovládaného oscilátoru (Voltage Controlled Oscillator; VCO) jako zdroje a zero-bias detektoru (ZBD) pro detekci, čímž se otevírá možnost postupu dále do oblastí vyšších polí / vyšších frekvencí. Dále je popsán postup získání ustáleného spektra z rapid-scan výsledků, známý jako Fourierovská dekonvoluce, a dále je zjistěn spinový dekoherenční čas vzorků pomocí srovnání experimentálních spekter s výsledky numericky vyřešených Blochových rovnic. Výsledné hodnoty jsou 50 ns pro BDPA a 12 ns pro LiPc.

Als nicht-invasive Methode bietet die magnetische Kernspinresonanztomographie durch ihre Vielzahl an messbaren Größen wie Wassergehalt und Flussgeschwindigkeiten gute Voraussetzungen, um funktionelle Abläufe in Pflanzen und insbesondere Pflanzenwurzeln zu untersuchen. Für funktionelle NMR-Mikroskopie notwendige Hardware und Methoden wurden in dieser Arbeit entwickelt und angewendet. Aufgrund der starken Suszeptibilitätsunterschiede in den Proben und der notwendigen Zeitauflösung für funktionelle Studien, lag das Hauptaugenmerk dabei auf Turbospinechomethoden (auch als RARE bekannt). Im Rahmen des Hardwareaufbaus wurde ein neuartiges, modulares Probenkopfkonzept entwickelt. Außerdem war es notwendig geeignete Probengefäße und Pflanzenhandlingsysteme zu entwerfen, die die Anbringung einer HF-Spule im Wurzelbereich erlauben. Für die Auswertung gemessener Parameterkarten wurde eine Software geschrieben, mit der interaktiv Mittelwerte entlang geschlossener Pfade berechnet werden können, angepasst an den grob radialsymmetrische Aufbau der Pflanzenwurzeln. Als Grundlage für biologische Aussagen anhand von T1-, T2- und Spindichtekarten wurden aus einer umfangreichen Literaturrecherche die bekannten Zusammenhänge zwischen diesen Parametern und physiologischen Größen zusammengestellt. Ergänzend wurde das Verhalten einer monoexponentiellen Beschreibung der Relaxation von mehr-Kompartimentsystemen und von deren Durchmischung untersucht. Eine Computersimulation der Diffusion zwischen Volumenschichten mit unterschiedlichen Relaxationszeiten wurde implementiert. Damit konnte gezeigt werden, dass die Reichweite der Durchmischung der messbaren Relaxationszeiten bei freier Diffusion abhängig ist von der Diffusionsweite, die nach der Einstein-Smoluchowski-Gleichung aus der jeweils lokalen Relaxationszeit resultiert. Damit ergibt sich eine grundsätzliche Limitierung der räumlichen Auflösung von Relaxationszeitkarten und auch des jeweiligen Relaxationszeitkontrastes in NMR-Bildern. Daneben erklärt der Effekt der durch Diffusion vermittelten Relaxation auch den hellen Ring, der in NMR-Bildern die Wurzeln in Nährlösung umgibt. Die hauptsächliche Anwendung der entwickelten Methodik auf biologische Fragestellungen bestand in der Untersuchung der Reaktion von Maiswurzeln auf Trockenstress. Erstmals konnten dabei im Rahmen dieser Arbeit Kavitationen der Wassersäule im Xylem von Wurzeln sowie deren Wiederbefüllung nach Wiederbewässerung der Pflanzen direkt beobachtet werden. Bei der weiteren systematischen Untersuchung zu Kavitationen gelang es auch, die bislang unbekannte Geschwindigkeit zu bestimmen (Größenordnung 1mm/min) mit der die kavitierten Bereiche von unten mit einer neuen Wassersäule gefüllt werden. Außerdem konnte mit Hilfe von Flussgeschwindigkeitskarten nachgewiesen werden, dass Gefäße mit Kavitationen nach der Wiederbefüllung ihre volle Funktionalität wiedererlangen können. Aus solchen Flusskarten konnte auch der Volumenfluss berechnet und z.B. mit der Transpirationsrate verglichen werden. Die gemessenen T1- und Spindichtekarten bieten viele Hinweise auf die Funktion der unterschiedlichen Gewebetypen der Wurzel während des Trockenstresses und bei der Wiederbefüllung. Insbesondere T1 erwies sich als aussagekräftiger Parameter für die Beurteilung von aufgetretenen Gewebeschäden. Als Grundlage für zukünftige Studien wurden verschiedene Messungen mit Kontrastmittel im Umgebungsmedium der Wurzeln durchgeführt, sowie eine 3D-Turbospinechosequenz implementiert, mit der auch die interne Struktur der Wurzeln und ihrer Verzweigungen dargestellt werden konnte. / MR imaging methods allow the non-invasive determination of values such as flow velocity and water content. Therefore, these methods provide a perfect means for the in-vivo examination of plants together with their surrounding medium. It was the aim of this PhD thesis to develop necessary hardware and software methods for functional studies on plant roots. Because of the large susceptibility differences of these samples and to provide a sufficient time resolution for functional studies especially RARE sequences were used and optimized for the examination of roots. Corn plants were grown in specially designed glass tubes which provided a narrow part for the inclusion of an RF Helmholtz coil. A new, patented concept for modular MR probes was designed. It allows the construction of probes that are adapted to the needs of certain samples like climate chamber probes for plants, without the limitation caused by fixed frequencies for the RF channels. A method to average values of tissues that are composed of concentric layers, like corn roots, or exhibit radial value gradients was implemented. An intense literature research about the known dependency of T1 and T2 on physiologic aspects of plant tissue was performed, resulting in a compilation of relaxation influencing effects. This compilation serves as a basis for the interpretation of the biological experiments. Further theoretical considerations dealt with the effect of a mono exponential description of the relaxation within multi compartment systems and after mixing the contents of these compartments. A computer algorithm was implemented to simulate the free diffusion between volumes that exhibit different relaxation values. It could be shown that transition regions of "mixed" relaxation values occur on the edges of those volume regions. The width of these transition regions can be determined by the Einstein-Smoluchowski-Equation for the diffusion displacement, using the underlying relaxation values as the diffusion time. This effect is a fundamental limitation to the spatial resolution of relaxation maps and to the contrast that those relaxation values create in MR images. Based on this finding, the cause for the bright ring that surrounds roots within nutrient solution in MR images could be explained. It results from the diffusion driven in-flow of quickly relaxing magnetisation from the outer part of the roots into the free solution. The most important biological results of this PhD thesis concern the reaction of plant roots to drought stress and rewatering. In the context of these drought stress experiments, cavitations of the sap in the xylem vessels on the roots could be observed for the first time using MR. In addition, the refilling of these cavitated vessels was monitored systematically. It was possible to measure the velocity of the newly ascending sap level, which was calculated to be in the order of 1mm/min. Using flow imaging, it was also possible to confirm the regained functionality of the refilled vessels for the first time. Based on flow maps, also the volume flow could be calculated and e.g. could be compared to the transpiration rate of the plants. The T1 and spin density maps acquired during the stress experiments give information about the function of the different tissues during desiccation and rewatering. Especially a strong decrease in T1 in the cortex of certain roots could be correlated with an irreversible damage to the tissue. To provide a further basis for future studies, experiments on the uptake of the MR contrast agent Gd-DTPA by the roots were performed. Also a 3D RARE microscopy sequence was implemented and used to follow the inner structure of the branching of a side root.

Universiẗat, Diss., 2002--Freiburg (Breisgau). / Erscheinungsjahr an der Haupttitelstelle: 2002.

The topic of this thesis is spin doctoring. It understands terms "spin" and "spin doctoring" as deliberate manipulation with public opinion by means of communication. The thesis includes an account of relevant concepts as are public relations, propaganda or corporate spin. It describes academical approaches to this issue. The authors criticize especially a corruptive influence of spin doctoring on democratic society and manipulative nature of public relations, but they offer possibilities of counteraction against these practices as well. The thesis considers both historical and recent manifestations of spin doctoring. Many examples analysed in this thesis concerns political environment of the Great Britain. Techniques and practices of spin doctoring such as "third party technique", "astroturfing" or "denigration campaings" are thoroughly explained. The perspective of semiotics and spin doctoring as manipulation with sign within social environment are concerned. The conflict between critics of spin doctoring and representatives of public relations is interpreted as discoursive discrepancy and both the antagonist discourses are analyzed. One chapter is devoted to spin doctoring within pharmaceutical industry. The practices and techniques of spin doctoring are interpreted in detail on this example....

L'imagerie par résonance magnétique (IRM) est un outil remarquable pour le diagnostic clinique, aussi bien pour l'imagerie cérébrale que pour l'imagerie cardiaque et abdominale. En IRM cardiaque, deux problèmes sont récurrents : la non reproductibilité des cycles cardiaques et le mouvement respiratoire. L'IRM cardiaque morphologique est généralement faite avec une séquence composée d'une préparation longue, visant à annuler le signal du sang pour accentuer le contraste au niveau du myocarde, et de l?acquisition à proprement parler. Ces acquisitions sont généralement faites en mésodiastole (phase de relaxation passive du coeur) ce qui permet de satisfaire les contraintes liées à l'annulation du sang et d'éviter les problèmes liés aux non reproductibilités des cycles cardiaques car la mésodiastole est longue. Il est donc difficile de satisfaire les contraintes liées à l?annulation du sang pour faire les acquisitions en télésystole (phase où le coeur est contracté) à cause des non reproductibilités cardiaques car la télésystole est courte. Afin de passer outre ces limitations et de pouvoir acquérir ces mêmes images morphologiques en télésystole, nous proposons une nouvelle méthode adaptative qui permet à la fois de placer la fenêtre d'acquisition de manière optimale et de satisfaire les contraintes liées à l'annulation du sang. Une application de cette méthode a également été mise en place pour estimer et comparer les temps de relaxation transversale (T2) entre télésystole et mésodiastole. Pour la gestion prospective du mouvement respiratoire, le point crucial est d'estimer les mouvements en temps réel en perturbant au minimum les signaux de résonance magnétique. Pour ce faire nous proposons une méthode basée sur l'estimation paramétrique des mouvements en temps réel à partir des signaux physiologiques disponibles (ceintures respiratoires et ECG). Cette méthode a été testée et les résultats montrent son intérêt et sa fiabilité par rapport aux erreurs faites au niveau du mouvement. Une méthode de reconstruction incluant les mouvements a également été utilisée pendant ces travaux afin de faire de l'imagerie en télésystole en respiration libre et d'utiliser d'autres types de capteurs respiratoires comme certains signaux de résonance magnétique. Ainsi pendant ces travaux, des méthodes adaptatives ont été mises en place afin de mieux gérer le mouvement et de prendre en compte les spécificités de chaque patient. Ces travaux ouvrent la voie de l'imagerie par résonance magnétique adaptative pleinement fonctionnelle dans un contexte clinique / Magnetic resonance imaging (MRI) is a valuable tool for the clinical diagnosis for brain imaging as well as cardiac and abdominal imaging. In cardiac MRI, there are two challenging issues: the non reproducibility of cardiac cycles and respiratory motion. Morphological cardiac MRI is generally performed with a pulse sequence composed of a long preparation, to cancel the blood signal and thus enhance the contrast of the myocardium, and the acquisition itself. These acquisitions are performed during the mid-diastolic rest (relaxation period of the heart) to satisfy constraints to cancel the blood signal and to avoid problems linked to the cardiac non reproducibility because the mid-diastolic rest is long. Consequently, to acquire images in end-systolic rest (when the heart is fully contracted) while taking into account constraints to cancel the blood signal is not straight forward due to cardiac non reproducibility because the end-systolic rest is short. To overcome these limitations and to acquire images in end-systolic rest, a new adaptive method is introduced that allows to optimally placing acquisition windows while taking constraint for the cancellation of the blood signal into account. This method was applied to measure and compare transverse relaxation time (T2) between end-systolic and mid-diastolic rests. For prospective respiratory motion correction, the crucial point is to estimate motion in real-time without perturbing MR signal used for imaging. In order to solve this issue, a new method is introduced aiming at estimating motion parameters in real-time based on physiological signals such as respiratory bellows and ECG. This method is evaluated and results show its interest and its reliability regarding motion estimation errors. A reconstructions algorithm is also used in order to perform cardiac imaging during the end-systolic rest in free breathing and to use different kind of respiratory motion sensors such as MR signals. Hence, during this research work, several adaptive method were developed to get a better management of motion and to take into account specificity of each patient. These works open the way of fully functional adaptive magnetic resonance imaging in a clinical situation

The topic of this thesis is spin doctoring. It understands terms "spin" and "spin doctoring" as deliberate manipulation with public opinion by means of communication. The thesis includes an account of relevant concepts as are public relations, propaganda or corporate spin. It describes academical approaches to this issue. The authors criticize especially a corruptive influence of spin doctoring on democratic society and manipulative nature of public relations, but they offer possibilities of counteraction against these practices as well. The thesis considers both historical and recent manifestations of spin doctoring. Many examples analyzed in this thesis concerns political environment of the Great Britain. Techniques and practices of spin doctoring such as "third party technique", "astroturfing" or "denigration campaings" are thoroughly explained. The perspective of semiotics and spin doctoring as manipulation with signs within social environment are concerned. The conflict between critics of spin doctoring and representatives of public relations is interpreted as discoursive discrepancy and both the antagonist discourses are analyzed. One chapter is devoted to spin doctoring within pharmaceutical industry. The practices and techniques of spin doctoring are interpreted in detail on this example....

Lobtention dun bon contraste en imagerie médicale est un pré-requis à un examen de qualité. Limagerie médicale basée sur la résonance nucléaire magnétique utilise diverses substances magnétiques comme agent de contraste. Le développement dagents de contraste à la fois plus performants et plus économiques sappuie fortement sur létude fondamentale des propriétés magnétiques de divers matériaux potentiellement utilisables. Dans ce travail, deux voies ont été poursuivies. La première partie est consacrée à des matériaux à transition de spin, qui pourraient être utilisés comme agents de contraste en résonance magnétique, pour autant que leur température de transition soit voisine de celle du corps humain. En effet, ces matériaux ont la particularité de posséder deux états magnétiques différents et, sous linfluence dune perturbation telle que la pression ou la température, peuvent passer dun état à lautre, à savoir létat paramagnétique ou diamagnétique. Les complexes de fer(II) étudiés sont basés sur des ligands tri-pyrazolyl borate et méthane. Une autre voie suivie pour améliorer le diagnostic médical est le développement et lutilisation de nanoparticules magnétiques fonctionnelles pour la détection et/ou le traitement des cellules cancéreuses. Dans la deuxième partie de ce travail, les propriétés magnétiques de nanoparticules ferriques préparées par deux méthodes différentes sont investiguées. La spectroscopie Mössbauer est largement utilisée dans cette thèse et les résultats obtenus par cette technique constituent la contribution principale de lauteur au travail. Cette technique, basée sur la fluorescence résonnante sans recul des rayons gamma, permet létude des interactions hyperfines de matériaux solides contenant du fer. Appliquée aux matériaux à transition de spin et aux nanoparticules, deux champs dapplication bien distincts, la spectroscopie Mössbauer fournit des informations structurelles et magnétiques. Elle complémente admirablement dautres techniques macroscopiques et microscopiques, comme la magnétométrie, la microscopie électronique et la diffraction des rayons X. Les autres techniques qui ont été utilisées par lauteur sont la magnétométrie et la relaxation des muons. Cest la première fois, que cette dernière technique est introduite dans léventail des techniques exploitées à lUniversité de Liège.

The underlying theory of “Spin” of an electron and its associated inter-actions causing internal fields and spectral shift to bulk-magnetism iswell established now. Our understanding of spin properties is significant andmore useful than ever before. In recent years there seems to be an enormousinterest towards application oriented materials that harness those spin prop-erties. Theoretical simulations remain in a position to “assist or pilot” theexperimental discovery of new materials.In this work, we have outlined available methodologies for spin coupling inmulti-reference and DFT techniques. We have benchmarked multi-referencespin-Hamiltonian computation in isoelectronic diradicals - Trimethylenemethane(TMM) and Oxyallyl. Also with DFT, parameters are predicted with anewly discovered TMM-like stable diradicals, reported to have large positiveexchange interactions. Excellent agreement were obtained and our findingsemphasize that the dipole-dipole interactions alone can predict the splittingof triplet states and that DFT spin procedures hold well in organic species.We have extended our spin-studies to a highly application oriented ma-terial - nanographene. Using our novel spin-parameter arguments we haveexplained the magnetism of graphene. Our studies highlight a few signifi-cant aspects - first there seems to be a size dependency with respect to thespin-Hamiltonian; second, there is a negligible contribution of spin-orbit cou-pling in these systems; third, we give a theoretical account of spin restrictedand unrestricted schemes for the DFT method and their consequences forthe spin and spatial symmetry of the molecules; and, finally, we highlightthe importance of impurities and defects for magnetism in graphene. Wepredict triplet-singlet transitions through linear response TDDFT for thetris(8-hydroxyquinoline) aluminium complex, an organic molecule shown tohave spintronics applications in recent experiments. Our spin studies werein line with those observations and could help to understand the role of thespin-coupling phenomena. / QC 20120531