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Targeting mycophenolate mofetil for graft-versus-host disease prophylaxis after allogenic blood stem cell transplantation

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / In this work we investigated the potentiality of batch injection analysis with square-wave voltammetry (BIA-SWV) detection for simultaneous determination of Zn and naphazoline (NAF) and batch injection analysis with multiple pulse amperometric (BIA-MPA) detection for simultaneous determination of NAF and pheniramine (FEN) or NAF and chlorpheniramine (CLO). In both methods, boron-doped diamond (BDD) was used as working electrode. For the simultaneous determination of Zn and NAF by BIA-SWV, the following conditions have been optimized: supporting electrolyte: acetate buffer 0.05 mol L-1 (pH = 4.7), injection volume: 100 μL, deposition time (Zn): 5 s, deposition potential (Zn) -1.5 V, : 100 s-1, a: 60 mV, ΔEs: 6 mV. Under these conditions, the method showed linear response range between 10 and 60 μmol L-1 for Zn (r = 0.992) and between 3.0 e 21 μmol L-1 for NAF (r = 0.999), high analytical frequency (70 injections h-1) and LOD of 0.126 μmol L-1 and 0.04 μmol L-1 for Zn and NAF, respectively. In the study of repeatability (n = 20), the calculated RSD were 0.98% and 0.97% for Zn and NAF, respectively. The simultaneous determination of NAF and FEN or NAF and CLO by BIA-MPA was performed with the application of three sequential pulses in function of time to the BDD electrode using Britton-Robinson Buffer solution 0.12 mol L-1 (pH = 10.0) as supporting electrolyte. At +1.1 V/50 ms, FEN or CLO was detected (oxidation) without interference of NAF. At +1.3 V/50 ms, both compounds (FEN + NAF or CLO + NAF) were oxidized. The current of NAF can then be obtained by subtraction of the currents detected during application of both potential pulses using a correction factor. The proposed method presented good ability (RSD = 1.7 and 4.0% for FEN and NAF; 2.1% and 3.6% for CLO and NAF, respectively; n=20); high analytical frequency (110 injections h-1), linear concentration range between 16 e 100 μmol L-1 for FEN and CLO (r > 0.996) and between 2 e 15 μmol L-1 for NAF (r > 0.997). The LOD calculated were 0.367, 0.361 e 0.148 μmol L-1, for FEN, CLO and NAF, respectively. The proposed methods were used for determination of these compounds in pharmaceutical samples. The obtained results were statistically similar to that obtained by HPLC (NAF, FEN and CLO) and atomic spectroscopy (Zn). / No presente trabalho investigou-se a potencialidade do sistema de análise por injeção em batelada com detecção por voltametria de onda quadrada (BIA-SWV) para determinação simultânea de Zn e nafazolina (NAF) e do sistema análise por injeção em batelada com detecção por amperometria de múltiplos pulsos (BIA-MPA) para determinação simultânea de NAF e feniramina (FEN) ou NAF e clorfeniramina (CLO). Em ambos os métodos, diamante dopado com boro (BDD) foi usado como eletrodo de trabalho. Para determinação simultânea de Zn e NAF empregando BIA-SWV, as seguintes condições foram otimizadas: eletrólito de suporte: tampão acetato 0,05 mol L-1 (pH = 4,7), volume de injeção: 100 μL, tempo de deposição (Zn): 5 s, potencial de deposição (Zn): -1,5 V, : 100 s-1, a: 60 mV, ΔEs: 6 mV. Nestas condições, o método apresentou faixa linear de resposta entre 10 e 60 μmol L-1 para Zn (r = 0,992) e entre 3,0 e 21 μmol L-1 para NAF (r = 0,999), frequência analítica de 70 injeções h-1 e limites de detecção de 0,126 μmol L-1e 0,04 μmol L-1 para Zn e NAF, respectivamente. No estudo de repetibilidade (n = 20), os DPRs foram calculados 0,98% e 0,97% para Zn e NAF, respectivamente. A determinação simultânea de NAF e FEN ou NAF e CLO por BIA-MPA foi realizada através da aplicação de dois pulsos de potenciais em função do tempo ao eletrodo de BDD usando tampão BR 0,12 mol L-1 (pH = 10) como eletrólito suporte. Em +1,1 V/50 ms, FEN ou CLO foram oxidadas livre da interferência de NAF. Em +1,3 V/50ms, ambos os compostos (NAF + FEN ou NAF + CLO) foram oxidados. A corrente proveniente da oxidação da NAF foi obtida pela subtração entre as correntes detectadas em ambos os pulsos de potenciais com auxílio de um fator de correção (FC). O método proposto apresentou boa estabilidade (DPR = 1,7 e 3,95% para FEN e NAF; 2,1 e 3,6% para CLO e NAF, respectivamente; n=20), alta frequência analítica (110 injeções h-1), faixa linear de resposta entre 16 e 100 μmol L-1 para FEN e CLO (r > 0,996) e entre 2 e 15 μmol L-1 para NAF (r > 0,997). Os limites de detecção foram de 0,367, 0,361 e 0,148 μmol L-1 para FEN, CLO e NAF, respectivamente. Os métodos propostos foram usados na determinação destes compostos em formulações farmacêuticas. Os resultados obtidos com os métodos propostos foram estatisticamente similares aos obtidos por HPLC (NAF, FEN e CLO) ou absorção atômica (Zn). / Mestre em Química

Targeting mycophenolate mofetil for graft-versus-host disease prophylaxis after allogenic blood stem cell transplantation:II Deckblatt III Gutachterblatt IV Widmung V Inhaltsverzeichnis VI.1 Publikation VI.2 Original-Artikel VII Abkürzungsverzeichnis VII.1 Selbständigkeitserklärung VII.2 Erklärung über den Eigenanteil bei Erstellung des Manuskriptes VII.3 Lebenslauf VII.4 Danksagung VII.5 Thesen

The goal of this research was to describe the nature, occurrence and extent to which integration preceded normative and institutional transformation in the SANDF and therefore in its Military Police, thereby demonstrating how in its aftermath, integration has become a recipe for disaster, casting a spell on further transformation within the military. The research also aimed at bringing the reader face-to-face with the daily struggles of Africans in the SANDF, by focusing on one of the smallest divisions of the military, the Military Police Agency (MPA). The research project was limited to all reported interviews and questionnaire responses of eighty five participants of the Southern Military Police Region (S MPR), excluding the S MPR HQ as well as the MPA HQ. A total of eighty five respondents out of a total strength of 172 S MPR composition, took part in the sample. Seventy nine participated in the questionnaire, fifty one in the interview and a total of forty five participated in both. Interviews were used as follow-up sessions to respondents' questionnaire answers. While the questionnaire was structured, the interview was semi-structured, allowing members to comment, object, affirm or question the process of transformation both in the SANDF and in the MPA. In keeping with the qualitative research method, the semi-structured interview enabled the mapping of categories, trends and patterns in the responses. It was found that MK and APLA cadres who integrated into the ex-Naval MPs surpassed their counterparts in the ex-Army MPs, by far. The two groups are incomparable, in rank level, experience, training, attitude and knowledge of the organisation. It was further discovered that most practices that had taken place before 1999 at W CSC and still continued within the MPA, negate SANDF policy and are criminal. Prejudice, racism, obscene language and gender insensitivity were rife, forming part of institutional culture. It is recommended that Weitzer's proposed solution for the transformation of coercive institutions be considered. It is a thoroughgoing transformation of the security apparatus through a legal framework because civil control is not enough to guarantee the pre-eminence of the democratic forces. / Criminology / M.A (Criminology)

La Manche orientale représente une zone économique importante qui supporte diverses activités anthropiques comme le tourisme, le transport maritime et l’exploitation de ressources vivantes ou minérales. De plus, cette région possède un riche patrimoine biologique illustré par sa grande diversité d’habitats. Les Aires Marines Protégées (AMP) sont souvent évoquées comme un instrument de gestion permettant d’aménager l’exploitation durable de ces ressources marines, dans le cadre d’une gestion écosystémique intégrée et responsable. Si les Etats ont pour obligation de créer des réseaux d’AMPs dans leurs eaux nationales, chacune d’elles est souvent localisée au cas par cas. Afin de coordonner la mise en place des différents réseaux d’AMPs, une démarche de planification spatiale systématique de la conservation est de plus en plus encouragée. Cette démarche a pour but de proposer un réseau d’AMP qui soit cohérent, même dans un contexte transfrontalier, comme c’est le cas en Manche orientale. Les travaux de recherche menés lors de cette thèse apportent ainsi une contribution scientifique à la mise en cohérence de l’aménagement des activités anthropiques avec les objectifs de conservation de l’écosystème marin de Manche orientale. Dans le cadre d’une approche de conservation intégrée, toute la biodiversité de la Manche orientale doit être représentée. Pour cela, en complément des typologies benthiques existantes dans la zone, une typologie des masses d’eau a été proposée et validée avec différents jeux de données d’espèces pélagiques. Marxan et Zonation, deux logiciels largement répandus en planification de la conservation ont été comparés dans le processus de conception du réseau d’AMP en Manche orientale. La conclusion a été que Marxan serait le logiciel utilisé pour la suite des analyses. En effet, ce logiciel est conçu pour atteindre clairement les cibles de conservation, ce qui facilite l’interprétation des résultats.Puis une étape essentielle de planification de la conservation a été réalisée à travers une analyse des lacunes (gap analysis) à l’échelle de la Manche orientale. Elle a permis de montrer que le réseau d’AMP existant atteint les cibles de conservation calculées dans cette thèse et qu’il couvre 33% de la Manche orientale. Il faut toutefois noter que l’étude des possibles lacunes au niveau de la gestion des AMPs n’a pu être réalisée de façon approfondie car la majorité de ces AMPS ne possèdent pas encore de plan de gestion défini.Finalement, l’influence de l’intégration des activités humaines dans le processus de conception du réseau d’AMP a été explorée grâce à l’utilisation de données d’effort de pêche et de données de débarquements. De plus, d’autres informations sur le trafic maritime, les extractions de granulats marins et les potentielles zones d’éoliennes en mer ont été ajoutées pour prendre en compte la totalité des usages et réglementation qui génèrent des contraintes spatiales en Manche orientale. / The eastern English Channel is a significant economic area that supports a number of human-based activities, such as tourism and recreational activities, international ports and shipping, and the extraction of both living and mineral resources. In addition, the region supports a number of important marine biological features and large habitat diversity. Marine Protected Areas (MPAs) are increasingly used as a management tool to foster a sustainable exploitation of marine resources in an ecosystem based management framework. All European countries have a legal obligation to develop MPA networks in their national waters. However, there has to date been only limited attempts to coordinate the design and positioning of such networks at an international level and the use of a systematic conservation planning approach is now recommended. This process aims to propose a coherent MPA network, even in a trans-boundary context as in the eastern English Channel (EEC). The studies conducted in this thesis contribute to the scientific knowledge needed to support both anthropogenic activities and conservation objectives in the eastern English Channel.The representation of the whole biodiversity of the eastern English Channel is important in a context of an integrated conservation approach. With this objective, to complete the existing benthic typologies, a pelagic typology was produced and validated with various pelagic species distribution data to ensure that the total biodiversity of the eastern English Channel would be considered.Marxan and Zonation, two widely used conservation planning software packages that provide decision support for the design of reserve systems were compared in the MPA network design process in the EEC. It was found that Marxan was most suitable for subsequent analyses in this thesis because it found reasonably efficient and clear solutions to the problem of selecting a system of spatially cohesive sites that met a suite of biodiversity targets, and the results were easily interpretable.Then, as it is an essential step in a conservation planning approach, a gap analysis was realized at the scale of the EEC. The currently proposed network met conservation targets proposed in this thesis and was found to cover 33% of the EEC. However, a correct assessment of management gaps was not possible as a major part of these MPA do not have management rules yet.Finally, the influence of the human activity data on the MPA design process was studied using landings and fishing effort data. Other information on maritime traffic, aggregate extraction or offshore windmills zones, and on-going MPA projects were also added to consider the whole set of uses and regulations that generate spatial constraints in the eastern English Channel.

The goal of this research was to describe the nature, occurrence and extent to which integration preceded normative and institutional transformation in the SANDF and therefore in its Military Police, thereby demonstrating how in its aftermath, integration has become a recipe for disaster, casting a spell on further transformation within the military. The research also aimed at bringing the reader face-to-face with the daily struggles of Africans in the SANDF, by focusing on one of the smallest divisions of the military, the Military Police Agency (MPA). The research project was limited to all reported interviews and questionnaire responses of eighty five participants of the Southern Military Police Region (S MPR), excluding the S MPR HQ as well as the MPA HQ. A total of eighty five respondents out of a total strength of 172 S MPR composition, took part in the sample. Seventy nine participated in the questionnaire, fifty one in the interview and a total of forty five participated in both. Interviews were used as follow-up sessions to respondents' questionnaire answers. While the questionnaire was structured, the interview was semi-structured, allowing members to comment, object, affirm or question the process of transformation both in the SANDF and in the MPA. In keeping with the qualitative research method, the semi-structured interview enabled the mapping of categories, trends and patterns in the responses. It was found that MK and APLA cadres who integrated into the ex-Naval MPs surpassed their counterparts in the ex-Army MPs, by far. The two groups are incomparable, in rank level, experience, training, attitude and knowledge of the organisation. It was further discovered that most practices that had taken place before 1999 at W CSC and still continued within the MPA, negate SANDF policy and are criminal. Prejudice, racism, obscene language and gender insensitivity were rife, forming part of institutional culture. It is recommended that Weitzer's proposed solution for the transformation of coercive institutions be considered. It is a thoroughgoing transformation of the security apparatus through a legal framework because civil control is not enough to guarantee the pre-eminence of the democratic forces. / Criminology and Security Science / M.A (Criminology)

À l’interface terre/mer et nature/société, les littoraux sont des territoires complexes et très attractifs où se déploient divers usages et pratiques qui génèrent de nombreux conflits et dégradations. Il existe aujourd’hui un consensus global quant à la nécessité de préserver ces espaces et la biodiversité qu’ils abritent. Depuis plusieurs décennies, c’est la gestion intégrée de la mer et du littoral (GIML) qui est prônée à l’échelle internationale comme la solution pour répondre aux problématiques rencontrées sur les zones côtières. L’approche s’inscrit dans la démarche du développement durable et elle tente de réconcilier l’usage des ressources et la conservation de la biodiversité. Une profusion de projets a vu le jour un peu partout à travers le monde et beaucoup de moyens humains et financiers ont été mobilisés à cet effet. Mais elle rencontre des difficultés importantes aussi bien dans sa mise en pratique que dans son évaluation. Or ce dernier point est largement reconnu comme un outil indispensable dans la planification et la gestion des projets et des programmes. Cette thèse propose donc une méthode d’élaboration d’indicateurs pour le suivi et l’évaluation des politiques de GIML qui permet d’apprécier les écarts entre les ambitions de protection de l’environnement, de développement économique et de bien-être social qui sous-tendent l’approche et les actions réalisées sur le terrain. Pour ce faire, quatre études de cas dans la Caraïbe ont été choisies. Il s’agit du Parc marin de Saba, de la Soufrière Marine Management Area (Sainte-Lucie), du groupe Nature Seekers (Trinidad) et du contrat de baie de Fort-de-France (Martinique). Ces expériences sont toutes citées comme des réussites en termes de gestion intégrée du littoral et comme des exemples à suivre. Mais répondent-elles réellement aux objectifs de la démarche ? La grille d’analyse proposée permet d’avoir une autre lecture des résultats de ces processus et de tirer des enseignements plus généraux pour la mise en pratique de la GIML. / At the interface of land and sea, and at the interface of nature and society, coastal areas are complex and very attractive territories where diverse uses and practices generate many conflicts and degradations. There is now a global consensus on the need to preserve these areas and their biodiversity. For several decades, Integrated Coastal and Ocean Management (ICOM) has been advocated internationally as the approach to address the problems encountered in coastal areas. The approach is a key paradigm for the sustainable development of coastal zones and it tries to reconcile the use of resources with the conservation of biodiversity. A large number of projects have been implemented around the world and many human and financial resources have been mobilized for this purpose. But ICOM implementation and evaluation remain much of a challenge. This last point is widely recognized as an indispensable tool in project and program planning and management. This thesis therefore proposes a methodology for the development of indicators for the monitoring and evaluation of GIML initiatives, which makes it possible to appreciate the gaps between ambitions for environmental protection, economic development and social welfare. Underpin the approach and the actions carried out on the ground. To do so, four case studies in the Caribbean were selected. These include the Saba Marine Park, the Soufrière Marine Management Area (Saint Lucia), the Nature Seekers Group (Trinidad) and the ‘Contrat de baie’ of Fort-de-France (Martinique). These experiences are all cited as success stories in terms of integrated coastal management and as examples to follow. But do they really respond to the objectives of the approach? The proposed analysis grid provides a further reading of the results of these processes and provides more general lessons for the implementation of GIML.

A growing number of scientists are investigating applications of landscape ecology principles to marine studies, yet few coral reef scientists have examined spatial patterns across entire reefscapes with a holistic ecosystem-based view. This study was an effort to better understand reefscape ecology by quantitatively assessing spatial structures and habitat arrangements using remote sensing and geographic information systems (GIS). Quantifying recurring patterns in reef systems has implications for improving the efficiency of mapping efforts and lowering costs associated with collecting field data and acquiring satellite imagery. If a representative example of a reef is mapped with high accuracy, the data derived from habitat configurations could be extrapolated over a larger region to aid management decisions and focus conservation efforts. The aim of this project was to measure repeating spatial patterns at multiple scales (10s m2 to 10s km2) and to explain the environmental mechanisms which have formed the observed patterns. Because power laws have been recognized in size-frequency distributions of reef habitat patches, this study further investigated whether the property exists for expansive reefs with diverse geologic histories. Intra- and inter-reef patch relationships were studied at three sites: Andavadoaka (Madagascar), Vieques (Puerto Rico), and Saipan (Commonwealth of the Northern Mariana Islands). In situ ecological information, including benthic species composition and abundance, as well as substrate type, was collected with georeferenced video transects. LiDAR (Light Detection and Ranging) surveys were assembled into digital elevation models (DEMs), while vessel-based acoustic surveys were utilized to empirically tune bathymetry models where LiDAR data were unavailable. A GIS for each site was compiled by overlying groundtruth data, classifications, DEMs, and satellite images. Benthic cover classes were then digitized and analyzed based on a suite of metrics (e.g. patch complexity, principle axes ratio, and neighborhood transitions). Results from metric analyses were extremely comparable between sites suggesting that spatial prediction of habitat arrangements is very plausible. Further implications discussed include developing an automated habitat mapping technique and improving conservation planning and delimitation of marine protected areas.

>Magister Scientiae - MSc / In this study PbSe quantum dots (QDs) were successfully synthesized via the organometallic and aqueous routes. Optical characterization was carried out using photoluminescence (PL) spectroscopy, structural and morphological characterization were carried out using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Energy-dispersive X-ray spectroscopy (EDS) was used to determine the composition of the QDs. All the synthesized QDs were found to have emissions within the near-infrared region of the spectrum (≥1000 nm) with most of them being less than 5 nm in size. The aqueous synthesized QDs had a perfect Gaussian emission spectrum with a FWHM of ~23 nm indicating pure band gap emission and narrow size distribution respectively. The QDs were determined to have a cubic rock-salt crystal structure consistent with bulk PbSe. The aqueous synthesized QDs were however not stable in solution with the QDs precipitating after approximately 48 h. The organometallic synthesized QDs were transferred into the aqueous phase by exchanging the surface oleic acid ligands with 11-mercaptoundecanoic acid ligands. The ligand exchanged QDs were however stable in solution for over two weeks. The effects of reaction parameters on the optical and structural properties of the organometallic synthesized QDs were investigated by varying the reaction time, temperature, ligand purity, lead and selenium sources. It was observed that larger QDs were formed with longer reaction times, with reactions proceeding faster at higher reaction temperatures than at lower temperatures. Varying the ligand purity was found to have minimal effects on the properties of the synthesized QDs. The lead and selenium sources contributed largely to the properties of the QDs with lead oxide producing spherical QDs which were smaller compared to the cubic QDs produced from lead acetate. TBPSe was seen to produce smaller QDs as compared to TOPSe. The cytotoxity of the synthesized QDs was determined following the WST-1 cell viability assay with the QDs being found to be non-toxic at all the tested concentrations