La curiethérapie est une technique ancienne utilisant des sources scellées de faible ou moyenne énergie, toujours pertinente aux plans thérapeutique et économique et toujours en évolution (e.g. curiethérapie à Haut Débit de Dose (HDD)). Cette modalité de traitement permet de délivrer une forte dose d'irradiation dans un volume-cible limité, et permet de minimiser le risque de cancer radio-induit en préservant les Organes à Risques (OAR). Cependant, elle génère des gradients de dose élevés rendant la dosimétrie in vivo délicate à mettre en oeuvre. Les écarts constatés entre doses délivrées et prescrites sont ainsi fréquemment supérieurs à l'écart maximal toléré par la réglementation (± 5%) en usage pour la radiothérapie externe conventionnelle et rendue obligatoire en France par décret depuis 2011. Ce travail de thèse s'est déroulé dans le cadre du projet ANR-TECSAN INTRADOSE et exploite les acquis technologiques antérieurs démontrés à l'issue du projet Européen MAESTRO et du projet ANR-TECSAN CODOFER, en particulier une instrumentation RL/OSL (Radioluminescence - Optically Stimulated Luminescence) multivoies réalisée et validée au plan préclinique dans le cadre du projet MAESTRO. Le projet INTRADOSE a pour objectif de démontrer la faisabilité d'une Dosimétrie In Vivo (DIV) intracavitaire par cathéter dosimétriques à fibres optiques et cristaux d'alumine Al2O3:C dans le but d'améliorer la sécurité des patients traités par Curiethérapie HDD. Ce nouveau type de détecteur permet de mesurer une distribution de doses (mulitpoints) proche des OAR, il présente un petit diamètre (<ou= 3 mm) destiné à un usage intracavitaire (e.g. insertion dans l'urètre), transparent, stable sous radiations et réutilisable après lecture des doses et stérilisation. Au cours de mon travail de thèse, nous avons développé ce nouveau cathéter dosimétrique basé sur la Luminescence Stimulée Optiquement utilisant les propriétés du cristal d'alumine. Différents tests ont permis d'évaluer sa faisabilité et sa compatibilité avec l'application médicale. Dans un second temps, des validations métrologiques et précliniques ont été menées dans le but de valider la réponse du détecteur dans le cadre d'une application de curiethérapie HDD de prostate. Ces différentes mesures ont été également confrontées à des simulations Monte-Carlo. Financé par l'Agence Nationale pour la Recherche - Technologies pour la Santé (ANR-TECSAN), ce projet associe le CEA LIST [Laboratoire de Mesures Optiques (LMO) et Laboratoire National Henri Becquerel (LNHB)] et le Centre de Lutte Contre le Cancer (CLCC) Léon Bérard (CLB), Centre Conseil et référent en Radiophysique / The brachytherapy is an old technique using sealed radioactive sources of low or average energy. This technique is still therapeutically and economically relevant today and always evolving (e.g. High Dose Rate (HDR) brachytherapy). This treatment enables to deliver a high dose of irradiation in a limited tumoral volume and enables to minimize the risk of radiation-induced cancer as preserving the Organs at Risks (OAR). However, this technique generates high dose gradients, which makes in vivo dosimetry difficult to implement. Hence, the deviations observed between doses delivered and prescribed are often up to the maximal deviation tolerated by the nuclear safety regulations (± 5%) in conformational radiotherapy. Those regulations have been made mandatory in France since 2011. This thesis has been done within the framework of the ANR-TECSAN INTRADOSE project and is based on the past technological benefits demonstrated during the MAESTRO European project and the ANR-TECSAN CODOFER project, in particular a RL/OSL multichannel instrumentation (Radioluminescence - Optically Stimulated Luminescence) made and validated in preclinical evaluation during the MAESTRO project. The purpose of the INTRADOSE project is to demonstrate the feasibility of the intracavitary In Vivo Dosimetry (IVD) by dosimetric catheter using optical fibers and alumina crystals Al2O3:C with the aim of improving the safety of patients treated by HDR brachytherapy. This new probe enables to measure a dose distribution (several points) close to the OAR, it offers a little diameter (<or= 3 mm) designed for an intracavitary use (e.g. to insert in the urethra), it is transparent, radiation stable and reusable after dose reading and sterilization. During this study, we have first developed this new dosimetric sensor based on the OSL using the properties of the alumina crystal. Several tests have been done in order to evaluate the feasibility and the compatibility with a medical application. Then, metrological and preclinical validations have been done in order to validate the response of the sensor for a prostatic application using HDR brachytherapy. These different measurements have also been compared to Monte-Carlo simulations. Funded by the Agence Nationale pour la Recherche - Technologies pour la Santé (ANR-TECSAN), this project combines the CEA LIST [Laboratoire de Mesures Optiques (LMO) and the Laboratoire National Henri Becquerel (LNHB)] and the Centre de Lutte Contre le Cancer (CLCC) Léon Bérard (CLB), advice center and advisor in radiophysics

Sur la côte du Sahel tunisien, les dépôts littoraux pléistocènes sont organisés en trois formations marines distinctes : Douira, Réjiche et Chebba définies par Paskoff et Sanlaville (1976) et redéfinies ultérieurement par Mahmoudi (1988) en unités lithostratigraphiques Douira, Khniss et Rejiche. Cependant, il n’a pas toujours été aisé de préciser la chronostratigraphie, la répartition géographique, et le rapport tectonique/eustatisme au cours du Pléistocène moyen et supérieur. La présente thèse se propose d’établir des subdivisions chronostratigraphiques régionales en s’appuyant sur la méthode de datation par luminescence IRSL. Les âges IRSL obtenus pour l’ensemble des dépôts littoraux pléistocènes (marins, lagunaires et dunaires) du Cap Bon oriental, du Sahel et du SE tunisien, s’échelonnent entre 335 ka et 66 ka. Ils se répartissent en six ensembles corrélés aux MIS 9, MIS 7, MIS 6/5, MIS 5.5, MIS 5.3/5.1 indifférencié et MIS 4. Ces âges IRSL démontrent qu’au Sahel, les dépôts marins littoraux pré-tyrrhéniens attribués à l’unité Douira sont corrélatifs de deux hauts niveaux marins interglaciaires distincts corrélables au MIS 9 et au MIS 7. Les âges IRSL des dépôts littoraux tyrrhéniens de la côte Est tunisienne (unités de Khniss et de Rejiche au Sahel), jusqu’ici attribués au MIS 5.5, s’inscrivent dans une chronologie beaucoup plus longue qui s’étend de la transition du MIS 6/5.5 au MIS 4. L’analyse tectonique de détail des populations de plans striés et des systèmes de joints qui affectent les unités littorales du Pléistocène moyen et supérieur (MIS 9 à MIS 4) a permis de préciser le régime tectonique et de déterminer les différents tenseurs de contrainte. Ceux-ci ont été classés et comparés en fonction des données chronostratigraphiques. Les nouvelles données lithostratigraphiques, chronologiques, sédimentologiques et tectoniques acquises dans le cadre de cette thèse sont ensuite replacées dans le contexte plus large de la Méditerranée occidentale. / Along the coast of the Tunisian Sahel, the Pleistocene littoral deposits are organized into three distinct marine formations: Douira, Rejiche and Chebba defined by Paskoff and Sanlaville (1976) and later redefined by Mahmoudi (1988) in terms of lithostratigraphic units Douira, Khniss and Réjiche. However, the chronostratigraphy, the distribution and the relationship between tectonics and eustatism during the Middle and Upper Pleistocene remained so far problematic. The present thesis offers to establish regional chronostratigraphic subdivisions by means of IRSL luminescence dating. The IRSL ages of the Pleistocene littoral deposits (marine, lagoonal and eolian) from the eastern Cap Bon peninsula, the Sahel area and Southeastern Tunisia, are ranging between 335 ka and 66 ka. They are subdivided into six units correlative with MIS 9, MIS 7, MIS 6/5, MIS 5.5, MIS 5.3/5.1 and MIS 4. These IRSL ages demonstrate that the pre-tyrrhenian littoral deposits assigned to the Douira unit belong to two distinct marine interglacial high stands correlative of MIS 9 and MIS 7. The IRSL results of the Tyrrhenian littoral deposits from eastern Tunisia (Khniss and Rejiche units), so far assigned to MIS 5.5, are consistent with a longer chronology that extends from the MIS 6/5 transition to MIS 4. The detailed tectonic analysis of fault populations and joint sets data affecting these Middle and Upper Pleistocene littoral units (MIS 9 to MIS 4) enabled to specify the tectonic regime. It also helped to ascertain the different stress tensors. The latter were classified and compared with each other according to the chronostratigraphic data. The new lithostratigraphic, chronological, sedimentological and tectonic data obtained in this thesis are then replaced in the context of the western Mediterranean basin.

Orientador: Arnaldo Alves Cardoso / Banca: José Anchieta Gomes Neto / Banca: Pedro Paulo Corbi / Banca: Ricardo Queiroz Aucélio / Banca: Mauro Korn / Resumo: Dentre os poluentes gasosos, o sulfeto de hidrogênio (H2S) e seus derivados - conhecidos como Compostos Reduzidos de Enxofre (CRE) - possuem grande destaque devido a sua alta toxicidade, propriedade corrosiva e participação em problemas ambientais diversos. Diferentes órgãos de controle de emissão ao redor do mundo estabelecem limites para a presença de H2S em diversos ambientes, variando de ppm (μg g-1) até baixo ppb (ng g-1). Para que estes limites sejam de fato cumpridos, é necessário que existam métodos analíticos que produzam resultados confiáveis para quantificar e, consequentemente, monitorar H2S em ambiente gasoso. Sensores ópticos apresentam vantagens como custo acessível, facilidade de operação, potencialidade para miniaturização e facilidade de aplicação em campo. Diversos compostos químicos com propriedades luminescentes tem sido utilizados como reagente para detecção de H2S, entretanto, a maioria é baseado em metais tóxicos (p.e. mercúrio), além de síntese complexa envolvendo várias etapas. Dentro desse contexto, a primeira parte desse trabalho envolve a síntese e caracterização de um composto inédito de paládio denominado bis (2-aminobenzóico) paládio (II), que possui comprimento de onda máximo de emissão em 410 nm quando excitado em 245 nm. Esse composto reage rapidamente com sulfetos aquosos e gasosos, liberando para o meio o ligante ácido 2-aminobenzóico, responsável pelo aumento da intensidade de fluorescência, proporcional a quantidade de sulfeto. O método desenvolvido possui limite de detecção de 0,075 μmol L-1 e 6,8 ppbv para sulfeto e H2S, respectivamente. A segunda etapa do trabalho envolveu a utilização da espectroscopia de absorção no infravermelho acoplada a uma nova geração de células gasosas, denominadas substrate-integrated hollow waveguides (i-HWG), para determinação em tempo real de H2S em matrizes gasosas. A determinação envolve a conversão imediata... / Abstract:Among the gaseous pollutants, hydrogen sulfide and its derivatives - also know as Reduced Sulfur Compounds (RSC) - have been attracting attention due their high toxicity, corrosive proprieties and involvement in several environmental issues. For this reason, there are many agencies worldwide that establish limits for the presence of H2S and RSC in several environmental compartments ranging from ppm (μg g-1) to low ppb (ng g-1). In order to enable the monitoring of these compounds in air, analytical methods must provide reliable and accurate results. Optical sensors appear particularly advantageous in terms of equipment cost, simplicity, easiness of operation, and potential for miniaturization. Several chemical compounds with luminescent proprieties have been used as reagent for sulfide detection. However, most of them are based on toxic metals and, furthermore, their synthesis contains many steps and generates toxic residues. In light of this context, a new palladium chelate compound - denominate bis (2-aminobenzoic) palladium (II) - was used to determinate sulfides in aqueous and gaseous samples as described in the first part of this thesis. The compound reacts with sulfides leading to the increase of the fluorescence intensity at 410 nm, when excited at 245 nm. The method was validated and enabled the determination of 0.075 μmol L- 1 and 6.8 ppbv for aqueous sulfide and gaseous H2S, respectively. The second part of this thesis involves the use of infrared spectroscopy coupled to a new generation of hollow waveguides, so-called substrate-integrated hollow waveguides, for the real-time monitoring of H2S in gaseous samples. The determination is based on the instantly and UV-based conversion of H2S to SO2, a very strong IR absorber at 1245 cm-1. The method enables the determination of 3 ppm of H2S. / Doutor

The immobilisation of uranium is an important issue within the nuclear industry due to contaminated land from accidental spillage, weapons testing or mining activities. Within the environment uranium is most commonly found in the +VI oxidation state as the mobile uranyl cation [UO2]2+. Alternatively, the +IV oxidation state can also be found in the environment, forming either an insoluble crystalline uraninite phase, or a more soluble molecular uranium(IV) species. Many endogenous subsurface bacteria can bind and accumulate actinide ions through biosorption and can reduce mobile uranyl(VI) species down to immobile uranium(IV) compounds and mineral phases. This work presents an investigation into the bioreduction process by two anaerobic Gram-negative bacteria, Geobacter sulfurreducens and Shewanella oneidensis MR-1. Luminescence spectroscopy is used to monitor the intensity of uranyl(VI) emission in situ over the course of a 24 hour bioreduction experiment with uranyl(VI) acetate as the electron acceptor and either acetate or lactate as the electron donor. An increase in intensity of the emission around hour three or four during the reduction, followed by an overall decrease, is attributed as the disproportionation of an unstable uranyl(V) intermediate. The role of inner and outer membrane c-typecytochromes as well as flavin secretion is also investigated using three deletion mutants of the S. oneidensis bacteria, which shows that in their absence, the reduction of uranyl(VI) does not occur over the course of 24 hours. The emission of uranium(IV) is also investigated during bioreduction in phosphate media and results show that emission can be observed in aqueous solutions at pH 7 pointing to the presence of a molecular product. One photon confocal and two photon fluorescence microscopy has been utilised for the very first time to directly optically image the bioreduction of uranyl(VI) in combination with luminescence lifetime mapping. The sorption of uranyl(VI) onto the surface of the bacteria with differing lifetimes indicates a direct interaction between uranyl(VI) and surface bound c-type cytochromes, since this variation was not observed in mutant S. oneidensis strains where the cytochromes were not present. Combined, these results have established the applicability of optical spectroscopy and microscopyin tracking the bioreduction of uranium in situ.

No description available.

O abafamento da luminescência em materiais contendo impureza de ferro é um fenômeno que ainda merece ser cuidadosamente investigado para que se possa chegar a uma descrição detalhada dos processos envolvidos. A matriz hospedeira escolhida para a realização deste trabalho foi o vidro 20 Al IND 2 o IND 3 ; 50 B IND 2 o IND 3 ; 30 BaO (mol%), do qual foram preparadas amostras às quais foram adicionadas quantidades variando de 10 POT -3 a 0,8 at% de Fe. A razão desta escolha prende-se ao fato de que a cinética de recombinação entre o centro de elétron do boro (BEC) e o centro de lacuna do boro e oxigênio (BOHC) em vidros boratos irradiados com raio-X a 77 K, responsável por uma intensa luminescência azul, já se conhece em detalhe através de resultados recentes de ressonância paramagnética eletrônica (RPE). A partir destes dados foi identificado cada um dos centros envolvidos na reação e foi possível acompanhar detalhadamente a cinética dos respectivos decaimentos térmicos. Com o apoio destas informações, os dados de termoluminescência (TL) deste trabalho puderam ser interpretados com maior segurança. Um arranjo experimental foi especialmente construído para a realização de medidas de TL na faixa de temperaturas entre 77 e 300 K. As medidas mostraram uma queda exponencial da TL em função da concentração de Fe. A supressão total da luminescência foi obtida para amostras contendo -0,1 at% de Fe. A energia de ativação média para a despopulação térmica do BEC foi obtida pelo método da rampa inicial da TL, resultando Ea = (0,22 ± 0,05) eV. Com base nos resultados de TL e RPE, apoiados pela teoria recente sobre o mecanismo de transições não radiativas, um modelo foi proposto para explicar o processo segundo o qual um íon Fe POT 3+ impede a ocorrência de processos radiativos de recombinação elétron-lacuna em um raio de ação que chega a 25 Å. Um elétron termicamente liberado do BEC, quando se aproxima do íon Fe3+ dentro do referido raio de ação, é capturado por um nível antiligante, fortemente deslocalizado, do orbital molecular de Fe3+ e oxigênio, sendo que o íon metálico ocupa a posição substitucional de um boro tetracoordenado. Imediatamente após a captura, ocorre um violento processo local de emissão de múltiplos fônons provocando o fenômeno da captura coerente de lacuna formando um éxciton, que rapidamente entra em colapso com nova emissão de fônons, provocando, assim, a recombinação elétron-lacuna sem irradiação luminescente. / The quenching of luminescence which occurs in materials containing iron impurity is yet a phenomenon worthy to be investigated towards a detailed description of the involved processes. The host matrix chosen was the 20 Al2 O3; 50 B2 O3; 30 Ba0 (mole%) glass, being the samples prepared containing varying amounts of Fe ranging from 10-3 to 0.8 at%. The reason of this particular choice is justified on the basis of detailed knowledge acquired from recent results of electron paramagnetic resonance (EPR), about the recombination kinetics of the boron electron center (BEC) and the boron-oxygen hole center (BOHC) in borate glasses X-irradiated at 77 K, responsible for an intense blue luminescence. From these data was identified each one of the centers involved in the reaction and it was possible to follow in detail the respective decay kinetics. With the support of these informations, the thermoluminescence (TL) data of this work could be better explained. An experimental array was specially built in order to carry out the TL measurements in the range of temperatures between 77 and 300 K. The measurements exhibited an exponencial decrease of the TL intensity in function of the Fe concentration. The total killing effect of the luminescence was obtained for samples containing -0.1 at% of Fe. The mean activation energy of the electron untrapping from the BEC was obtained with the TL initial-slope method, giving Ea = (0.22 ± 0.05) eV. On the basis on TL and EPR results and the support of recent theories about non-radiative transition mechanism, a model was proposed in order to explain the process involved when a Fe3+ ion prevents the occurrence of radiative electron-hole recombinations inside a volume of radius less than 25 K. A thermally released electron of BEC, when reaches the neighborhood of a Fe3+ ion inisde its radius of action, is trapped by an antibonding energy level, strongly delocalized, of the molecular orbital of Fe3+ and oxygen, where the metallic ion occupies the substitutional position of a tetra-coordinated boron. Immediately after the trapping, there occurs a violent local process of multiphonon emission giving rise to the phenomenon of the coherent hole capture creating an exciton, which collapses rapidly with a new emission of phonos, resulting therefore, in the electron-hole recombination without luminescent irradiation.

O abafamento da luminescência em materiais contendo impureza de ferro é um fenômeno que ainda merece ser cuidadosamente investigado para que se possa chegar a uma descrição detalhada dos processos envolvidos. A matriz hospedeira escolhida para a realização deste trabalho foi o vidro 20 Al IND 2 o IND 3 ; 50 B IND 2 o IND 3 ; 30 BaO (mol%), do qual foram preparadas amostras às quais foram adicionadas quantidades variando de 10 POT -3 a 0,8 at% de Fe. A razão desta escolha prende-se ao fato de que a cinética de recombinação entre o centro de elétron do boro (BEC) e o centro de lacuna do boro e oxigênio (BOHC) em vidros boratos irradiados com raio-X a 77 K, responsável por uma intensa luminescência azul, já se conhece em detalhe através de resultados recentes de ressonância paramagnética eletrônica (RPE). A partir destes dados foi identificado cada um dos centros envolvidos na reação e foi possível acompanhar detalhadamente a cinética dos respectivos decaimentos térmicos. Com o apoio destas informações, os dados de termoluminescência (TL) deste trabalho puderam ser interpretados com maior segurança. Um arranjo experimental foi especialmente construído para a realização de medidas de TL na faixa de temperaturas entre 77 e 300 K. As medidas mostraram uma queda exponencial da TL em função da concentração de Fe. A supressão total da luminescência foi obtida para amostras contendo -0,1 at% de Fe. A energia de ativação média para a despopulação térmica do BEC foi obtida pelo método da rampa inicial da TL, resultando Ea = (0,22 ± 0,05) eV. Com base nos resultados de TL e RPE, apoiados pela teoria recente sobre o mecanismo de transições não radiativas, um modelo foi proposto para explicar o processo segundo o qual um íon Fe POT 3+ impede a ocorrência de processos radiativos de recombinação elétron-lacuna em um raio de ação que chega a 25 Å. Um elétron termicamente liberado do BEC, quando se aproxima do íon Fe3+ dentro do referido raio de ação, é capturado por um nível antiligante, fortemente deslocalizado, do orbital molecular de Fe3+ e oxigênio, sendo que o íon metálico ocupa a posição substitucional de um boro tetracoordenado. Imediatamente após a captura, ocorre um violento processo local de emissão de múltiplos fônons provocando o fenômeno da captura coerente de lacuna formando um éxciton, que rapidamente entra em colapso com nova emissão de fônons, provocando, assim, a recombinação elétron-lacuna sem irradiação luminescente. / The quenching of luminescence which occurs in materials containing iron impurity is yet a phenomenon worthy to be investigated towards a detailed description of the involved processes. The host matrix chosen was the 20 Al2 O3; 50 B2 O3; 30 Ba0 (mole%) glass, being the samples prepared containing varying amounts of Fe ranging from 10-3 to 0.8 at%. The reason of this particular choice is justified on the basis of detailed knowledge acquired from recent results of electron paramagnetic resonance (EPR), about the recombination kinetics of the boron electron center (BEC) and the boron-oxygen hole center (BOHC) in borate glasses X-irradiated at 77 K, responsible for an intense blue luminescence. From these data was identified each one of the centers involved in the reaction and it was possible to follow in detail the respective decay kinetics. With the support of these informations, the thermoluminescence (TL) data of this work could be better explained. An experimental array was specially built in order to carry out the TL measurements in the range of temperatures between 77 and 300 K. The measurements exhibited an exponencial decrease of the TL intensity in function of the Fe concentration. The total killing effect of the luminescence was obtained for samples containing -0.1 at% of Fe. The mean activation energy of the electron untrapping from the BEC was obtained with the TL initial-slope method, giving Ea = (0.22 ± 0.05) eV. On the basis on TL and EPR results and the support of recent theories about non-radiative transition mechanism, a model was proposed in order to explain the process involved when a Fe3+ ion prevents the occurrence of radiative electron-hole recombinations inside a volume of radius less than 25 K. A thermally released electron of BEC, when reaches the neighborhood of a Fe3+ ion inisde its radius of action, is trapped by an antibonding energy level, strongly delocalized, of the molecular orbital of Fe3+ and oxygen, where the metallic ion occupies the substitutional position of a tetra-coordinated boron. Immediately after the trapping, there occurs a violent local process of multiphonon emission giving rise to the phenomenon of the coherent hole capture creating an exciton, which collapses rapidly with a new emission of phonos, resulting therefore, in the electron-hole recombination without luminescent irradiation.

Chemiluminescence, the production of light from a chemical reaction, has found widespread use in analytical chemistry. Both tris (2, 2’-bipyridyl) ruthenium (II) and acidic potassium permanganate are chemiluminescence reagents that have been employed for the determination of a diverse range of analytes. This thesis encompasses some fundamental investigations into the chemistry and spectroscopy of these chemiluminescence reactions as well as extending the scope of their analytical applications. Specifically, a simple and robust capillary electrophoresis chemiluminescence detection system for the determination of codeine, O6-methylcodeine and thebaine is described, based upon the reaction of these analytes with chemically generated tris(2,2'-bipyridyl)ruthenium(III) prepared in sulfuric acid (0.05 M). The reagent solution was contained in a glass detection cell, which also held both the capillary and the cathode. The resultant chemiluminescence was monitored directly using a photomultiplier tube mounted flush against the base of the detection cell. The methodology, which incorporated a field amplification sample introduction procedure, realised detection limits (3a baseline noise) of 5 x 10~8 M for both codeine and O6-methylcodeine and 1 x 10~7 M for thebaine. The relative standard deviations of the migration times and the peak areas for the three analytes ranged from 2.2 % up to 2.5 % and 1.9 % up to 4.6 % respectively. Following minor instrumental modifications, morphine, oripavine and pseudomorphine were determined based upon their reaction with acidic potassium permanganate in the presence of sodium polyphosphate. To ensure no migration of the permanganate anion occurred, the anode was placed at the detector end whilst the electroosmotic flow was reversed by the addition of hexadimethrine bromide (0.001% m/v) to the electrolyte. The three analytes were separated counter to the electroosmotic flow via their interaction with a-cyclodextrin. The methodology realised detection limits (3 x S/N) of 2.5 x 10~7 M for both morphine and oripavine and 5 x 10~7 M for pseudomorphine. The relative standard deviations of the migration times and the peak heights for the three analytes ranged from 0.6 % up to 0.8 % and 1.5% up to 2.1 % respectively. Further improvements were made by incorporating a co-axial sheath flow detection cell. The methodology was validated by comparing the results realised using this technique with those obtained by high performance liquid chromatography (HPLC), for the determination of both morphine and oripavine in seven industrial process liquors. A complimentary capillary electrophoresis procedure with UV-absorption detection was also developed and applied to the determination of morphine, codeine, oripavine and thebaine in nine process liquors. The results were compared with those achieved using a standard HPLC method. Although over eighty papers have appeared in the literature on the analytical applications of acidic potassium permanganate chemiluminescence, little effort has been directed towards identifying the origin of the luminescence. It was found that chemiluminescence was generated during the manganese(III), manganese(IV) and manganese(VII) oxidations of sodium borohydride, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689 ± 5 nm and 734 ± 5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate or orthophosphoric acid environments respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K, exhibited two peaks with maxima at 688 nm and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution phase chemically induced phosphorescence of manganese(II). Thereby confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species. Additionally, these findings have had direct analytical application in that manganese(IV) was evaluated as a new reagent for chemiluminescence detection. The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 x S/N) for Mn(II), Fe(II), morphine and codeine of 5 x 10-8 M, 2.5 x 10-7 M, 7.5 x 10-8 M and 5 x 10-8M, respectively. The corrected emission spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm indicating that these chemiluminescence reactions also shared a common emitting species, excited manganese(II). Whilst several analytical problems were addressed in this thesis and answers to certain questions regarding the fundamentals of acidic potassium permanganate chemiluminescence were proposed, there are several areas that would benefit from further research. These are outlined in the final chapter of this thesis.

Les nanoparticules d'oxydes dopés par des lanthanides sont d'un intérêt particulier pour leur luminescence propre à la nature des ions dopants et non à la taille du matériau. La voie colloïdale est souvent la méthode la mieux adaptée pour obtenir des objets nanométriques, individualisés, bien cristallisés et dispersables dans un milieu donné avec une fluorescence optimisée. Toutefois, elle reste difficile à réaliser pour ces matériaux de température de cristallisation élevée et conduit à des nanocristaux dont les propriétés physiques sont généralement altérées par les défauts cristallins. Ce travail de thèse a ainsi été consacré à l'élaboration de nanoparticules YVO4:Ln parfaitement monocristallines et à l'étude de leurs propriétés optiques. Les nanocristaux formés sont issus d'une synthèse colloïdale suivie d'un traitement thermique dans une matrice de silice mésoporeuse. Les particules obtenues sont monocristallines, nanométriques (40 nm) et stables dans l'eau. Les spectres de luminescence des particules YVO4:Ln sont semblables à ceux des matériaux microniques. Avec un dopage par Eu3+, les rendements de luminescence atteignent 40%. Cette valeur, plus faible que pour le massif (68%), s'explique par la limitation induite par un indice de réfraction plus faible que dans le monocristal massif. Avec un codopage par Yb3+ et Er3+, le phénomène d'upconversion a été observé et étudié pour la 1ère fois en solution aqueuse. Ces nanoparticules sont des convertisseurs relativement efficaces de photons infrarouges en photons visibles. Les particules YVO4:Eu ont par ailleurs été fonctionnalisées pour être utilisées comme sondes biologiques.

Thesis (Doctor)--Technische Universiteit Delft, 2006. / Includes bibliography (p. 134-136).