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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
411

An investigation of the political factors contribution to floor crossing in the Malawi National Assembly : 2003-2009

Maganga, Anne Grace 06 1900 (has links)
Floor crossing was an unknown phenomenon in Malawi until the re-emergence of multiparty politics in 1994. Since then the number of MPs crossing the floor in the Malawi National Assembly has steadily increased from around twelve in 1994 to more than sixty in 2005. This practice has continued even today. However, the biggest incident of floor crossing took place in 2005 when the State President, Dr Bingu wa Mutharika, under the United Democratic Front (UDF) decided to abandon the party that sponsored him into office to form his own, the Democratic Progressive Party in February, 2005. Following him were several opposition MPs, a move which sparked a lot of tension in the National Assembly. The purpose of this study was to investigate political factors contributing to this phenomenon, and it was established that, among other factors, institutional weaknesses of political parties and gaps in the Constitution contributed significantly to floor crossing. / Political Science / M.A. (African Politics)
412

Détection de ruptures et mouvement Brownien multifractionnaire / Change Point Detection and multifractional Brownian motion

Fhima, Mehdi 13 December 2011 (has links)
Dans cette thèse, nous développons une nouvelle méthode de détection de ruptures "Off-line", appelée Dérivée Filtrée avec p-value, sur des paramètres d'une suite de variables aléatoires indépendantes, puis sur le paramètre de Hurst d'un mouvement Brownien multifractionnaire. Cette thèse est composée de trois articles. Dans un premier article paru dans Sequential Analysis nous posons les bases de la méthode Dérivée Filtrée avec p-value (FDpV) en l'appliquant à une suite de variables aléatoires indépendantes. La méthode a une complexité linéaire en temps et en mémoire. Elle est constituée de deux étapes. La première étape utilisant la méthode Dérivée Filtrée détecte les bons instants de ruptures, mais également certaines fausses alarmes. La deuxième étape attribue une p-value à chaque instant de rupture potentiel détecté à la première étape, et élimine les instants dont la p-value est inférieure à un certain seuil critique. Nous démontrons les propriétés asymptotiques nécessaires à la calibration de la méthode. L'efficacité de la méthode a été prouvé tant sur des données simulées que sur des données réelles. Ensuite, nous nous sommes attaqués à l'application de la méthode pour la détection de ruptures sur le paramètre de Hurst d'un mouvement Brownien multifractionnaire. Cela s'est fait en deux phases. La première phase a fait l'objet d'un article à paraitre dans ESAIM P&S où nous avons établi un Théorème Central Limite pour l'estimateur du paramètre de Hurst appelé Increment Ratio Statistic (IRS). Puis, nous avons proposé une version localisée de l'IRS et démontré un TCL local pour estimer la fonction de Hurst d'un mouvement Brownien multifractionnaire. Les preuves sont intuitives et se distinguent par leur simplicité. Elles s'appuient sur le théorème de Breuer-Major et une stratégie originale appelée "freezing of time". La deuxième phase repose sur un nouvel article soumis pour publication. Nous adaptons la méthode FDpV pour détecter des ruptures sur l'indice de Hurst d'un mouvement Brownien fractionnaire constant par morceaux. La statistique sous-jacent de l'algorithme FDpV est un nouvel estimateur de l'indice de Hurst, appelé Increment Zero-Crossing Statistic (IZCS) qui est une variante de l'IRS. La combinaison des méthodes FDpV + IZCS constitue une procédure efficace et rapide avec une complexité linéaire en temps et en mémoire. / This Ph.D dissertation deals with "Off-line" detection of change points on parameters of time series of independent random variables, and in the Hurst parameter of multifrcational Brownian motion. It consists of three articles. In the first paper, published in Sequential Analysis, we set the cornerstones of the Filtered Derivative with p-Value method for the detection of change point on parameters of independent random variables. This method has linear time and memory complexities, with respect to the size of the series. It consists of two steps. The first step is based on Filtered Derivative method which detects the right change points as well as the false ones. We improve the Filtered Derivative method by adding a second step in which we compute the p-values associated to every single potential change point. Then we eliminate false alarms, i.e. the change points which have p-value smaller than a given critical level. We showed asymptotic properties needed for the calibration of the algorithm. The effectiveness of the method has been proved both on simulated data and on real data. Then we moved to the application of the method for the detection of change point on the Hurst parameter of multifractional Brownian motion. This was done in two phases. In the first phase, a paper is to be published in ESAIM P&S where we investigated the Central Limit Theorem of the Increment Ratio Statistic of a multifractional Brownian motion, leading to a CLT for the time varying Hurst index. The proofs are quite simple relying on Breuer-Major theorems and an original freezing of time strategy.The second phase relies on a new paper submitted for publication. We adapted the FDpV method to detect change points on the Hurst parameter of piecewise fractional Brownian motion. The underlying statistics of the FDpV technology is a new statistic estimator for Hurst index, so-called Increment Zero-Crossing Statistic (IZCS) which is a variation of IRS. Both FDpV and IZCS are methods with linear time and memory complexities, with respect to the size of the series.
413

Kreuz und quer: Händel und Rossini, Paisiello und Paer

Schröder, Gesine 06 September 2010 (has links) (PDF)
Welche Bühnenfigur konnte in italienischen Opern um 1800 als Liebhaber oder als Verführer erfolgreicher sein als ein Counter oder ein Kastrat? Höchstens die als Mann verkleidete Frau. Auf sie flogen die Frauen in Frauenkleidern. Wer quer zum üblichen Geschlechterunterschied stand, war auch kompositorisch besonders attraktiv: Züge des einen Geschlechts mussten mit stimmtechnischen, d.h. auch körperlichen Bedingungen des anderen erreicht werden. Auf andere Weise sah sich der Komponist von einem den Geschlechtscharakter der Bühnenfigur gerade nicht verwischenden, sondern explizit festlegenden Genre herausgefordert, der Wahnsinnsszene. Der Text hatte nicht nur davon zu reden, dass die Figur wahnsinnig sei, die Musik musste es zeigen oder: es selber werden. Wahnsinnig wurde in den allermeisten Fällen nur die von einer Frau dargestellte Frau, und zudem war das Privileg solche Szenen zu übernehmen an eine oft besonders hohe Stimmlage gekoppelt. Welchen Schwierigkeiten der Komponist begegnete, wollte er das Genre von dem weiblichen auf das männliche Geschlecht transponieren, wird an einer der seltenen Opernszenen gezeigt, in denen ein Mann, zudem einer mit tiefer Stimme, wahnsinnig werden darf.
414

An investigation of the political factors contributing to floor crossing in the Malawi National Assembly : 2003-2009

Maganga, Anne Grace 06 1900 (has links)
Floor crossing was an unknown phenomenon in Malawi until the re-emergence of multiparty politics in 1994. Since then the number of MPs crossing the floor in the Malawi National Assembly has steadily increased from around twelve in 1994 to more than sixty in 2005. This practice has continued even today. However, the biggest incident of floor crossing took place in 2005 when the State President, Dr Bingu wa Mutharika, under the United Democratic Front (UDF) decided to abandon the party that sponsored him into office to form his own, the Democratic Progressive Party in February, 2005. Following him were several opposition MPs, a move which sparked a lot of tension in the National Assembly. The purpose of this study was to investigate political factors contributing to this phenomenon, and it was established that, among other factors, institutional weaknesses of political parties and gaps in the Constitution contributed significantly to floor crossing. / Political Science / M.A. (African Politics)
415

Kreuz und quer: Händel und Rossini, Paisiello und Paer: (Kleine Systematik des Stimmtauschs)

Schröder, Gesine 06 September 2010 (has links)
Welche Bühnenfigur konnte in italienischen Opern um 1800 als Liebhaber oder als Verführer erfolgreicher sein als ein Counter oder ein Kastrat? Höchstens die als Mann verkleidete Frau. Auf sie flogen die Frauen in Frauenkleidern. Wer quer zum üblichen Geschlechterunterschied stand, war auch kompositorisch besonders attraktiv: Züge des einen Geschlechts mussten mit stimmtechnischen, d.h. auch körperlichen Bedingungen des anderen erreicht werden. Auf andere Weise sah sich der Komponist von einem den Geschlechtscharakter der Bühnenfigur gerade nicht verwischenden, sondern explizit festlegenden Genre herausgefordert, der Wahnsinnsszene. Der Text hatte nicht nur davon zu reden, dass die Figur wahnsinnig sei, die Musik musste es zeigen oder: es selber werden. Wahnsinnig wurde in den allermeisten Fällen nur die von einer Frau dargestellte Frau, und zudem war das Privileg solche Szenen zu übernehmen an eine oft besonders hohe Stimmlage gekoppelt. Welchen Schwierigkeiten der Komponist begegnete, wollte er das Genre von dem weiblichen auf das männliche Geschlecht transponieren, wird an einer der seltenen Opernszenen gezeigt, in denen ein Mann, zudem einer mit tiefer Stimme, wahnsinnig werden darf.
416

共榮的想像:帝國日本與大東亞文學圈(1937-1945) / Imagining Co-Prosperity:Imperial Japan and the Literary Sphere of Great East Asia,1937-1945

李文卿, Lee, Wen Ching Unknown Date (has links)
本論文以1937年至1945年「中日戰爭」、「大東亞戰爭」時期為座標,透過考察大東亞共榮圈下的東亞經驗、記憶、文化與歷史的交錯問題。並試圖以宏觀的角度來檢視日本與亞洲各國的關係,從「跨界」的視域進行東亞文學與文藝體制之研究討論,探討關於日本的大東亞共榮圈之建構概念及其欲型塑的東亞文學觀,與大東亞共榮圈各地域對於此文學建構所衍伸出的知識、權力、文化關係的接受與質變。從日本因應戰爭的動員過程以及帝國主義思潮的發展脈絡中,可以窺見透過國家機器的運作模式,日本企圖在內地、殖民地及各佔領區中塑造「共同體」之想像,並欲透過此「共同體」的想像型塑出「大東亞共榮圈」的東亞一體之翼贊結構。另一方面,大東亞共榮圈中的各地域對於此「共榮想像」也各有不同的對應態勢,從中可以觀看出大東亞文學圈中的文學者們認同的游移,同時對於大東亞議題在不同的統治模式下所衍生出的不同之「協力」圖像。 本論文是以日本的帝國主義發展之脈絡為東亞文學圈的論述中心,並擇取大東亞共榮圈下的五個漢字使用地域為個案討論對象,包括了殖民地:台灣、朝鮮、傀儡政權:滿洲國、中國(華北、華中),以此討論日本文學共榮的表象與實際,以及東亞地區在大東亞想像下的文學樣貌。大東亞的文藝運動可以說是日本國家主義發展的衍生,包括文學者統合團體的誕生、筆部隊的派遣、報國文學的創作乃至於徵用作家的紀行報導,全都受到國家機器的操弄。「八紘一宇」支撐了日本的國體論述,在各個地域中並以日語教育取代血緣的系聯,欲藉由語言型構出「東亞民族」的一體性,同時透過各地域的日本文學者之創作,也顯現了此大東亞的視野,透過戰爭文學、勤勞文學、增產文學、國民文學各種文學書寫模式與文學生產過程,日本文學者們也從不同角度展現出帝國想像。此外,透過統合文學者的文學報國會之串連,也建構了大東亞文學圈的文學者們的「交流」系譜,各地域的文學者也在此文學場域中各自展開「文學共榮」的命題。 / This dissertation examines the entanglement of memory, history and cultural experience within the Greater East Asia Co-Prosperity Sphere during the Second Sino-Japanese War or Greater East Asia War between 1937 and 1945. From a comprehensive perspective of boundary crossing, this dissertation intends to study the conceptualization and formation of a unified East Asian literary ideal and its literary and cultural institutions by examining the discourse of a Greater East Asia Co-Prosperity Sphere in the context of Japanese Imperialism. It further explores the reception and transformation of knowledge, power, and cultural struggles shaped by this literary construction within the cultural sphere. Through the observation of the process of wartime mobilization and the development of imperial ideology, this dissertation reveals that the Japanese Empire intended to implant the image of an imagined community in Japan, the Japanese colonies, and occupied areas. By enlisting this imagined community, the Japanese Imperial would forge a cooperative institution, the Greater East Asia Co-Prosperity Sphere, within which “Asia is One.” On the other hand, intellectuals in different parts of Japanese East Asia adopted different positions in response to the imposition of this imagined Co-Prosperity Sphere. By scrutinizing their responses, we will discern these writers’ shifting positions and diverse strategies of “collaboration” under different types of rule and across various regions. The dissertation traces the progress of Japanese Imperialism as the discursive center of the East Asia Literary Sphere. Five regions from the Chinese character-using portions of the empire were chosen as case studies: Japanese colonies such as Taiwan, Korea, as well as puppet regimes like those in Manchukuo, and occupied North and Central China. By surveying the literary performances in these East Asian regions that were under the influenced of the discourse of Great East Asia, we could get past the surface and scrutinize the reality of the ideology of the Japanese Literary Co-Prosperity Sphere. The Greater East Asian Literary Movement was a byproduct of the development of Japanese nationalism. All literary activities were manipulated by the Japanese state apparatus, including the establishment of writers’ alliance, the dispatching of the Pen Writers’ Brigade, the writing of Patriotic Literature, as well as the reportage from Conscript Writers. The discourse of Hakkō ichiu (All the world under one roof) became the core of Japanese national ideology. Japanese became the sole language taught in schools throughout the Japanese empire in an attempt to replace ties of blood and ethnicity with a linguistic affiliation. Through this linguistiunity, Imperial Japan fostered the unity of an “East Asian ethnicity.” Writing in diverse genres such as War Literature, Labor Literature, Increasing Production Literature and National Literature, Japanese writers in different parts of East Asia manifested the imperialist dream of a Greater East Asia. Moreover, through the establishment of organizations such as the Association of Literary Patriotism, writers in the Greater East Asia Literary Sphere gained a legitimate channel to communicate and exchange their ideas on literature. In other words, East Asian writers constructed and developed their own discourses of “Literary Co-Prosperity” within this context.
417

Modelling the effects of changing habitat characteristics and spatial pattern on woodland songbird distributions in West and Central Scotland

Creegan, Helen P. January 2005 (has links)
This study investigated bird distributions in relation to local habitat and landscape pattern and the implications which habitat fragmentation may have for woodland birds. There were two sections to the research: an experimental study investigating bird gap crossing behaviour across distances of five to 120m; and an observational study modelling woodland bird distributions in relation to local habitat and landscape scale variables in two study areas (East Loch Lomond and the Central Scotland Forest). In the experimental study it was hypothesised that bird willingness to cross gaps will decrease with increasing gap distance even at home-range scales and that the rate of decline will vary interspecifically in relation to bird morphology. Song thrush mobbing calls played at woodland edges in the West of Scotland were used to attract birds across gaps and results were compared with the response along woodland edges. Data were obtained for four species: chaffinch, coal tit, robin and goldcrest. The decline in response with distance across gaps and along woodland edge was modelled for each species using generalized linear modelling. Maximum gap crossing distances ranged from 46m (goldcrest) to 150m (extrapolated value for the chaffinch). Goldcrests responded more readily through woodlands. There was no difference between woodland edge and gap response for the coal tit. Robins and chaffinches however responded more readily across gaps than through woodland. When different response indices were plotted against bird mass and wing area, results suggested that larger birds with bigger wings responded more readily across gaps than through woodland. It is suggested that this relates to differences in bird manoeuvrability within woodlands and ability to evade a predator in gaps. Fragmentation indices were calculated for an area of the Central Scotland Forest to show how willingness to cross different gap distances influences perception of how fragmented the woodlands are in a region. Results are discussed in the context of the creation of Forest Habitat Networks. The data for the observational section of the work was from bird point counts for 200 sample points at East Loch Lomond in 1998 and 2000 and 267 sample points in the Central Scotland Forest in 1999. In addition a time series of point count data was available for 30 sample points at East Loch Lomond. Additional data was gathered for ten sample points (1998) and two sample points (2000) at East Loch Lomond to investigate effects of observer, time and weather on count data. Generalized linear and generalized additive modelling was carried out on these additional data. Results indicated that biases due to the variation in time and weather conditions between counts existed in the pure count data but that these were eliminated by reducing data to presence and absence form for analysis. Species accumulation curves indicated that two counts per sample point were insufficient to determine species richness. However a sufficiently large proportion of the species was being detected consistently in two counts of ten minutes duration for it to be valid to model them in relation to habitat and landscape variables. Point count data for East Loch Lomond in 1998 (ELL98) and the Central Scotland Forest in 1999 (CSF99) for the wren, treecreeper, garden warbler, robin, blue tit, blackbird, willow warbler, coal tit, goldcrest, great tit, and song thrush were analysed using generalized additive modelling. In addition models were built for the blackcap (CSF99) and the siskin, redstart and wood warbler (ELL98). Where all relationships were identified as linear, models were rebuilt as GLMs. Models were evaluated using the Area Under the Curve (AUC) of Receiver Operating Characteristic (ROC) plots. AUC values ranged from 0.84-0.99 for ELL98 and from 0.76-0.93 for CSF99 indicating high predictive accuracy. Habitat variables accounted for the largest proportion of explained variation in all models and could be interpreted in terms of bird nesting and feeding behaviour. However additional variation was explained by landscape scale and fragmentation related (especially edge) variables. ELL98 models were used to predict bird distributions for Loch Lomond in 2000 (ELL00) and for the CSF99. Likewise the CSF99 models were used to predict distributions for ELL98 and ELL00. Predicted distributions had useful application in many cases within the ELL site between years. Fewer cases of useful application arose for predicting distributions between sites. Results are discussed in the context of the generality of bird environment relationships and reasons for low predictive accuracy when models are applied between sites and years. Models which had useful application for ELL00 were used to predict bird distributions for 2025 and 2050 at East Loch Lomond. Habitat and landscape changes were projected based on the proposed management for the site. Since woodland regeneration rates are difficult to predict, two scenarios were modelled, one assuming a modest amount of regeneration and one assuming no regeneration. Predictions derived from the ELL98 models showed broad-leaved species increasing in distribution while coniferous species declined. This was in keeping with the expected changes in the relative extent of broad-leaved and coniferous habitat. However, predictions from the CSF99 models were often less readily explicable. The value of the modelling approach is discussed and suggestions are made for further study to improve confidence in the predictions.
418

Modélisation de l’incertitude sur les trajectoires d’avions / Uncertainty modeling on aircraft trajectories

Fouemkeu, Norbert 22 October 2010 (has links)
Dans cette thèse, nous proposons des modèles probabilistes et statistiques d’analyse de données multidimensionnelles pour la prévision de l’incertitude sur les trajectoires d’aéronefs. En supposant que pendant le vol, chaque aéronef suit sa trajectoire 3D contenue dans son plan de vol déposé, nous avons utilisé l’ensemble des caractéristiques de l’environnement des vols comme variables indépendantes pour expliquer l’heure de passage des aéronefs sur les points de leur trajectoire de vol prévue. Ces caractéristiques sont : les conditions météorologiques et atmosphériques, les paramètres courants des vols, les informations contenues dans les plans de vol déposés et la complexité de trafic. Typiquement, la variable dépendante dans cette étude est la différence entre les instants observés pendant le vol et les instants prévus dans les plans de vol pour le passage des aéronefs sur les points de leur trajectoire prévue : c’est la variable écart temporel. En utilisant une technique basée sur le partitionnement récursif d’un échantillon des données, nous avons construit quatre modèles. Le premier modèle que nous avons appelé CART classique est basé sur le principe de la méthode CART de Breiman. Ici, nous utilisons un arbre de régression pour construire une typologie des points des trajectoires des vols en fonction des caractéristiques précédentes et de prévoir les instants de passage des aéronefs sur ces points. Le second modèle appelé CART modifié est une version améliorée du modèle précédent. Ce dernier est construit en remplaçant les prévisions calculées par l’estimation de la moyenne de la variable dépendante dans les nœuds terminaux du modèle CART classique par des nouvelles prévisions données par des régressions multiples à l’intérieur de ces nœuds. Ce nouveau modèle développé en utilisant l’algorithme de sélection et d’élimination des variables explicatives (Stepwise) est parcimonieux. En effet, pour chaque nœud terminal, il permet d’expliquer le temps de vol par des variables indépendantes les plus pertinentes pour ce nœud. Le troisième modèle est fondé sur la méthode MARS, modèle de régression multiple par les splines adaptatives. Outre la continuité de l’estimateur de la variable dépendante, ce modèle permet d’évaluer les effets directs des prédicteurs et de ceux de leurs interactions sur le temps de passage des aéronefs sur les points de leur trajectoire de vol prévue. Le quatrième modèle utilise la méthode d’échantillonnage bootstrap. Il s’agit notamment des forêts aléatoires où pour chaque échantillon bootstrap de l’échantillon de données initial, un modèle d’arbre de régression est construit, et la prévision du modèle général est obtenue par une agrégation des prévisions sur l’ensemble de ces arbres. Malgré le surapprentissage observé sur ce modèle, il est robuste et constitue une solution au problème d’instabilité des arbres de régression propre à la méthode CART. Les modèles ainsi construits ont été évalués et validés en utilisant les données test. Leur application au calcul des prévisions de la charge secteur en nombre d’avions entrants a montré qu’un horizon de prévision d’environ 20 minutes pour une fenêtre de temps supérieure à 20 minutes permettait d’obtenir les prévisions avec des erreurs relatives inférieures à 10%. Parmi ces modèles, CART classique et les forêts aléatoires présentaient de meilleures performances. Ainsi, pour l’autorité régulatrice des courants de trafic aérien, ces modèles constituent un outil d’aide pour la régulation et la planification de la charge des secteurs de l’espace aérien contrôlé. / In this thesis we propose probabilistic and statistic models based on multidimensional data for forecasting uncertainty on aircraft trajectories. Assuming that during the flight, aircraft follows his 3D trajectory contained into his initial flight plan, we used all characteristics of flight environment as predictors to explain the crossing time of aircraft at given points on their planned trajectory. These characteristics are: weather and atmospheric conditions, flight current parameters, information contained into the flight plans and the air traffic complexity. Typically, in this study, the dependent variable is difference between actual time observed during flight and planned time to cross trajectory planned points: this variable is called temporal difference. We built four models using method based on partitioning recursive of the sample. The first called classical CART is based on Breiman CART method. Here, we use regression trees to build points typology of aircraft trajectories based on previous characteristics and to forecast crossing time of aircrafts on these points. The second model called amended CART is the previous model improved. This latter is built by replacing forecasting estimated by the mean of dependent variable inside the terminal nodes of classical CART by new forecasting given by multiple regression inside these nodes. This new model developed using Stepwise algorithm is parcimonious because for each terminal node it permits to explain the flight time by the most relevant predictors inside the node. The third model is built based on MARS (Multivariate adaptive regression splines) method. Besides continuity of the dependent variable estimator, this model allows to assess the direct and interaction effects of the explanatory variables on the crossing time on flight trajectory points. The fourth model uses boostrap sampling method. It’s random forests where for each bootstrap sample from the initial data, a tree regression model is built like in CART method. The general model forecasting is obtained by aggregating forecasting on the set of trees. Despite the overfitting observed on this model, it is robust and constitutes a solution against instability problem concerning regression trees obtained from CART method. The models we built have been assessed and validated using data test. Their using to compute the sector load forecasting in term to aircraft count entering the sector shown that, the forecast time horizon about 20 minutes with the interval time larger than 20 minutes, allowed to obtain forecasting with relative errors less than 10%. Among all these models, classical CART and random forests are more powerful. Hence, for regulator authority these models can be a very good help for managing the sector load of the airspace controlled.
419

Elementary solute-solvent interactions and the photophysical properties of photoacids

Premont-Schwarz, Mirabelle 12 August 2013 (has links)
Photosäuren sind aromatische Alkohole, sogenannt aufgrund der Erhöhung ihrer Azidität, die aus der elektronischen Anregung folgt. Allerdings muss ein plausibles Verständnis der Prozesse, die zu der Erhöhung der Azidität führen noch etabliert werden. Zu diesem Zweck wird die Photophysik zweier Photosäuren, 1-Naphthol (1N) und 2-Naphthol (2N), untersucht. Mit Hilfe der Femtosekunden-UV-Anrege/IR-Abtast-Spektroskopie wird die OH-Streckschwingung sowohl im Grundzustand als auch im angeregten Zustand gemessen. Die intrinsische elektronische Ladungsverteilung, die aufgrund der Anregung in der Säure auftritt, in apolaren Lösungsmitteln untersucht. Der Vergleich mit Resultaten eines theoretischen Modells stellte einwandfrei fest, dass eine geringe Ladungsverteilung in der Photosäure auftritt. Die OH-Streckschwingung von wasserstoffverbrückten Komplexen zwischen 2N und Acetonitril wird gemessen. Obwohl experimentell gefunden wurde, dass der angeregte Zustand verglichen mit dem Grundzustand eine nahezu doppelt so große solvatochromatische Verschiebung zeigt, scheitern theoretische Modelle daran, diese Ergebnisse wiederzugeben. Die Ladungstransferreaktion im angeregten Zustand von 1N und 2N zu halogenierten Lösungsmitteln wird zur Abfrage der elektronischen Dichte am aromatischen Ring nach Anregung verwendet. Wurde ermittelt, dass verglichen mit dem unkomplexierten Molekül die Elektrontransferrate in einem wasserstoffverbrückten Komplex mit Acetonitril 10 mal höher ist. Auf diese Weise hat sich der Einfluss der Wasserstoffbrückenbindung auf das Ausmaß der Ladungsverteilung gezeigt. Mittels zeitaufgelöster Anisotropie, Fluoreszenz und IR-Messungen war es möglich festzustellen, dass die ultraschnelle ( / Photoacids are aromatic alcohols, characterized by a dramatic increase in acidity upon electronic excitation. A coherent view of the processes giving rise to this increase in acidity has yet to be established. To this effect, the photophysics of photoacids 1-naphthol (1N) and 2-naphthol (2N) are investigated. Using femtosecond UV pump-IR probe spectroscopy, the OH stretch vibration in both the ground and excited-state is measured. The intrinsic electronic charge redistribution in the acid upon excitation is investigated in non-polar solvents where specific interactions are absent. Comparison with results from a theoretical model based on the Pullin-van der Zwan-Hynes perturbative approach established that little charge redistribution occurs in the photoacid. The OH stretch vibration of hydrogen-bonded complexes of 2N with acetonitrile is measured. While it was found experimentally that the excited-state is characterized by a solvatochromic response that is almost twice as large as in the ground-state, the theoretical model failed to reproduce these results. Instead, the calculations predict no significant differences between the behaviour of the two states. The excited-state charge transfer reaction of 1N and 2N to halogenated solvents is used as a probe for the electronic density on the aromatic ring upon excitation. The charge transfer rate for the hydrogen-bonded complex with acetonitrile is found to be ten times higher than for the uncomplexed molecule. In this way, the influence of a hydrogen-bond on the extent of charge redistribution was evinced. Using time resolved anisotropy, fluorescence and IR measurements, it was determined that ultrafast (
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Reação de acessos de Capsicum spp. a Colletotrichum sp., agente causal da antracnose das Solanáceas. / Reaction of accesses of Capsicum spp. to Colletotrichum sp., causal agent of anthracnose.

Pereira, Mônica Juliani Zavaglia 04 March 2005 (has links)
A importância do cultivo de espécies do gênero Capsicum vem crescendo nos últimos anos no Brasil, e consequentemente, a ocorrência de doenças torna-se um problema relevante. A antracnose é a mais comum e destrutiva doença de Capsicum no Brasil e em vários países, podendo ocasionar perdas de até 100%. Seu controle usando resistência genética seria altamente desejável. O objetivo deste trabalho foi (i) caracterizar a reação à antracnose de 90 acessos de Capsicum annuum, 30 de C. baccatum, 16 de C. chinense e um de C. frutescens; (ii) estabelecer a correlação da reação à antracnose entre plântulas e frutos de Capsicum e; (iii) avaliar a reação à antracnose das progênies F3RC1 (C.annuum x C. chinense - resistente) x C. annuum e F2RC2 [(C. annuum x C. chinense) x C. annuum] x C. annuum. Para as inoculações, foram utilizados quatro isolados do fungo Colletotrichum sp. provenientes de pimentão e um isolado de pimenta, obtidos de folhas e frutos doentes. As suspensões de inóculo foram preparadas na concentração de 1 x 106 conídios/ml, separadamente para cada isolado. Após ajustada a concentração das suspensões, estas foram misturadas, a fim de reduzir efeitos de possível variabilidade patogênica dos isolados. O delineamento utilizado foi inteiramente casualizado com 20 repetições para plântulas e 15 repetições para frutos verdes destacados. Os ensaios foram conduzidos duas vezes. Nas inoculações das plântulas, foi adicionado 5% de caldo de cana à suspensão, como fonte exógena de energia ao patógeno. A inoculação nas plântulas foi realizada no estádio de primeira folha verdadeira completamente expandida, pela aspersão da suspensão de esporos até o ponto de escorrimento. As plântulas foram mantidas em câmara úmida por 24 horas antes e 72 horas após a inoculação. O ensaio foi instalado em sala climatizada com temperatura de 26 +/- 2°C e fotoperíodo de 12 horas. Foi avaliada a severidade de doença, usando uma escala de notas e também a incidência da doença, com base na percentagem de plântulas doentes. A inoculação nos frutos foi realizada pela deposição de uma gota de 20 µl da suspensão de esporos na parte mediana dos frutos. Posteriormente, com o auxílio de uma agulha entomológica, foi realizado um ferimento abaixo da gota. Os frutos inoculados foram mantidos em câmara úmida durante o período de avaliação. As avaliações foram realizadas pela mensuração do diâmetro médio das lesões, período latente, velocidade de crescimento da lesão e incidência. Baseando-se na avaliação dos frutos para classificação da reação, identificou-se apenas um acesso de C. annuum como resistente (n°233 - Jalapeno), um de C. baccatum (n°222 - BGH 4176) e dois de C. chinense (n°105 - Bode e n°141 - Pimenta n°2). Os demais acessos foram suscetíveis. Não houve correlação entre a reação de plântulas e frutos. As plântulas apresentaram menor quantidade de doença, em relação aos frutos. As progênies F3RC1 (3G, 4A, 4B, 4F, 4H, 5H, 6B, 6F, 8B, 8E, 8F, 9B, 9D, 9E, 9J, 10A, 13D, 13F, 14A, 14C, 16D, 16I, 17B, 19B) e as progênies F2RC2 (33F e 40G) não apresentaram lesões no estádio de frutos. Avançou-se geração nas progênies com reação de resistência em frutos, e suas populações F4RC1 e F3RC2 foram avaliadas no estádio de plântulas. Constatou-se variabilidade para a reação de antracnose nestas populações, com expressão de menor severidade e possibilidade de obter cultivares de pimentas e pimentões resistentes à antracnose. / Capsicum cultivation is an increasing activity in Brasil, and, in conseqüence, disease occurence is becoming more frequent. Anthracnose is the most common and desctructive disease of Capsicum in Brasil and other countries. Losses of 100% due to the disease are very frequent. Control of anthracnose using genetic resistance can be very suitable. The aim of this work was (i) to describe the reaction of 90 accesses of Capsicum annuum, 30 of C. baccatum, 16 of C. chinense and one of C. frutescens to anthracnose (ii) to establish the correlation of the reaction to anthracnose between seedlings and fruits of Capsicum and (iii) to evaluate the reaction to anthracnose of the progenies F3RC1 (C.annuum x C. chinense - resistant) x C. annuum and F2RC2 [(C. annuum x C. chinense - resistant) x C. annuum] x C. annuum. Four isolates of Colletotrichum sp. from pepper and one isolate from hot pepper were used for the inoculations, at a concentration of 1 x 106 spores/ml. After adjustment of the concentration of each suspension, they were mixed, in order to reduce possible effects of pathogenic variability among the isolates. The experimental design used was of completely randomized blocks with 20 and 15 replications for seedlings and green-ripe fruits inoculations, respectively. For the inoculation in seedlings, sugarcane juice at 5% was added to the spore suspensions, which were sprayed on the leaves of the seedlings at one-leaf stage. The seedlings were kept in a moist chamber for 24 hours before and 72 hours after the inoculation, at 26 +/-2°C and 12 hours photoperiod, inside a growth chamber. To evaluate anthracnose on the inoculated plants, disease incidence and disease severity were considered. The last variable was rated based on a 1 to 5 scale, according to the amount of disease on the seedlings. The fruits were inoculated with a 20 µl droplet of the spore suspensions. After depositing the inoculum, the fruits were wounded with a needle at the inoculation point and kept at 24 +/- 2°C, inside covered plastic containers. The evaluation was done based on lesions diameter, latent period, growth rate of lesions and incidence. The fruits evaluations were used for classifying the accesses reactions. Only one access of C. annuum (n°233 - Jalapeno), one of C. baccatum (n°222 - BGH 4176) and two of C. chinense (n°105 - Bode and n°141 - Pimenta n°2) were considered resistant. The remaining accesses varied in degrees of susceptibility. Positive correlation between levels of disease in seedlings and fruits were not significant. The seedlings showed less amount of disease in relation to fruits. The progenies 3G, 4A, 4B, 4F, 4H, 5H, 6B, 6F, 8B, 8E, 8F, 9B, 9D, 9E, 9J, 10A, 13D, 13F, 14A, 14C, 16D, 16I, 17B, 19B (population F3RC1) and 33F and 40G (F2RC2) did not show lesions at the fruit stage. Generations were advanced in this population and populations F4RC2 and F3RC2 were evaluated at seedling stage. These seedlings showed variability for reaction to anthracnose, with lower severity, suggesting possibility of selection for resistance in Capsicum varieties.

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