La caractérisation juste et reproductible en isotopie et en concentration des radioéléments est l’une des thématiques essentielles des laboratoires d’analyse dans le domaine du nucléaire. Afin de minimiser les temps de manipulation en boite à gants des personnels et la production de déchets radioactifs liés à l’analyse de combustibles nucléaires, il est nécessaire de proposer des solutions efficaces et innovantes. Depuis quelques années, la miniaturisation des systèmes séparatifs constitue l’un des axes de développement majeurs de la chimie analytique et ces microsystèmes constituent certainement une des solutions pour répondre aux exigences de l’analyse nucléaire. Ce travail a pour objectif la conception d’une plateforme analytique miniaturisée et à usage unique, dédiée a la séparation des lanthanides, issus des combustibles usés, en amont de leur analyse par spectrométrie de masse. Destiné à remplacer une étape de séparation chromatographique au centre d’un processus analytique de trois étapes, le nouveau protocole basé sur l’isotachophorèse (ITP) doit satisfaire un cahier des charges précis. Les propriétés de complexation des lanthanides ont d’abord été exploitées afin d’obtenir avec un agent chélatant unique et rigoureusement sélectionné, l’acide 2-hydroxy-2-methylbutyrique (HMBA), la sélectivité intra période nécessaire à leur séparation complète par ITP. Basées sur des modèles théoriques existants, des études complémentaires, notamment des paramètres influençant la résolution, ont permis l’amélioration des performances globales du système ainsi que son dimensionnement. Pour réduire drastiquement le volume de déchets liquides secondaires (solutions de rinçage) et la manipulation de matériaux et de matériels radioactifs, le protocole a été implanté sur un microsystème polymérique jetable en COC, spécialement développé pour cette application. Ce microsystème a ensuite été couplé à un spectromètre de masse a multi collection et source à plasma à couplage inductif pour mesurer les rapports isotopiques / The accurate and reproducible characterization of radioactive solutions in isotope composition and concentration is an essential topic for analytical laboratories in the nuclear field. In order to reduce manipulation time in glove box and production of contaminated wastes, it is necessary to propose innovative and efficient solutions for these analyses. Since few years, microchips are a major field of development in analytical chemistry and those devices could provide a solution which fits the needs of nuclear industry. The aim of this work is to design a disposable analytical micro-device devoted to lanthanide separation from spent nuclear fuel before their analysis in mass spectrometry. Designed to be used in place of a separation process by liquid chromatography which is involved in a three step protocol, the new protocol based on isotachophoresis (ITP) keeps compatible with the other two steps. The complete separation of lanthanides by ITP was obtained by the use of only one chelating compound rigorously selected: the 2-hydroxy 2-methyl butyric acid (HMBA). The main parameters involved in solute resolution were defined from the theoretical models of ITP and experimental studies of the influence of these parameters allowed to optimize the geometry of the system and to improve its performances. To suppress cleaning of the system and, consequently, to strongly reduce both liquid waste volume and handling radioactive material, the ITP protocol was transferred in a polymeric (COC) disposable microchip especially developed for this purpose

Este trabalho apresenta um estudo sistemático sobre síntese, caracterização e análise térmica aplicada a óxidos mistos dos tipos TR2NiO4 [TR = La, Eu e Y (III)] e TRNiO3 [TR = Pr, Nd e Sm (III)]. Os primeiros óxidos foram obtidos a partir da decomposição térmica de acetatos de terras raras e níquel utilizando-se três métodos distintos: (1) mistura mecânica; (2) evaporação do solvente e (3) cristalização com acetona. Os acetatos simples e binários foram caracterizados por análise elementar, espectroscopia de absorção na região do infravermelho, difração de raios X, TG/DTG, DSC e DTA. Os resultados revelaram a formação de sais binários quando utilizaram-se os métodos 2 e/ou 3. Os produtos da decomposição térmica foram basicamente os óxidos individuais e após tratamento térmico obteveram-se os óxidos desejados. Os óxidos TRNiO3 foram preparados através de três métodos diferentes: (1) mistura de óxidos; (2) precipitação simultânea de hidróxidos e (3) processo sol-gel. Estas amostras foram sinterizadas em temperaturas 650 ≤ T ≤ 1000°C e sob pressões de até 70 atm de O2, caracterizadas por difração de raios X, resistividade elétrica, microscopia eletrônica de varredura e calorimetria exploratória diferencial. Os resultados indicaram que o método sol-gel produziu óxidos monofásicos. Os outros dois métodos, mistura de óxidos e hidróxidos, produziram a fase desejada e traços dos óxidos individuais. Desta forma, concluiu-se que a escolha do método a ser utilizado é fundamental para a obtenção do óxido misto desejado. / This work reports a systematic study on the synthesis, characterization and thermal analysis applied of mixed oxides type-TR2NiO4 [TR = La, Eu e Y (III)] e typeTRNiO3 [TR = Pr, Nd e Sm (III)]. The first oxides were prepared through thermal decomposition of rare earth and nickel acetates, which were synthesized by three methods: (1) mechanical mixture; (2) solvent evaporation and (3) crystallization with addition of acetone. The simply and binary acetates were characterized by elementare analyses, infrared spectroscopy, X ray diffraction, TG/DTG, DSC and DTA. The results revealed formation of binary salts when was used the second and/or third methods. The products of thermal decomposition were single oxides, but after thermal treatment were obtained the single phase of materials. The last oxides were prepared through three different methods: (1) mixture of oxides; (2) simultaneous precipitation of hydroxides and (3) sol-gel process. Samples were sintered at temperatures between 650 ≤ T ≤ 1000°C and under oxygen pressures until 70 atm, characterized by X ray diffraction, electrical resistivity, scanning electron microscopy and differential scanning calorimetry. The results revealed that the sol-gel method produced single phase oxides. The other two methods, mixture of oxides and hydroxides, led to have this phase with traces of single oxides. Therefore, it was concluded that the method used is fundamental to get the desired mixed oxides.

Lanthanide elements display many remarkable and exciting properties which explain their widespread use in a number of very important biomedical tools like efficient MRI contrast agents or luminescent probes for highly sensitive assays of bioanalytes amongst other fields of application. In this context, the aim of the present work was to prepare and characterize lanthanide complexes of two ligands that feature a linear or a macrocyclic chelating unit compactly grafted onto a 1,10-phenanthroline derived moiety (phenDTPA and PhenHDO3A). The ditopic nature of the ligands allows the selective incorporation of a d6 metal ion and a lanthanide one in close proximity. The resulting rigid heterobimetallic supramolecular species show useful properties and constitute potential MRI contrast agents or new luminescent compounds depending on the type of the lanthanide and transition metal ions employed: for example, the selfassembly process of gadolinium(III) chelates around an iron(II) ion brings a remarkable increase of their relaxivity, a key parameter for use in MRI. On the other hand, association of a ruthenium and and a near infrared emitting 4f ion like ytterbium(III) gives mixed d-f structures able to harvest visible light and convert it into near infra-red signal. Visible light luminescent pH probes were also obtained with Eu3+ or Tb3+ phenHDO3A complexes.

La caractérisation juste et reproductible en isotopie et en concentration des radioéléments est l'une des thématiques essentielles des laboratoires d'analyse dans le domaine du nucléaire. Afin de minimiser les temps de manipulation en boite à gants des personnels et la production de déchets radioactifs liés à l'analyse de combustibles nucléaires, il est nécessaire de proposer des solutions efficaces et innovantes. Depuis quelques années, la miniaturisation des systèmes séparatifs constitue l'un des axes de développement majeurs de la chimie analytique et ces microsystèmes constituent certainement une des solutions pour répondre aux exigences de l'analyse nucléaire. Ce travail a pour objectif la conception d'une plateforme analytique miniaturisée et à usage unique, dédiée a la séparation des lanthanides, issus des combustibles usés, en amont de leur analyse par spectrométrie de masse. Destiné à remplacer une étape de séparation chromatographique au centre d'un processus analytique de trois étapes, le nouveau protocole basé sur l'isotachophorèse (ITP) doit satisfaire un cahier des charges précis. Les propriétés de complexation des lanthanides ont d'abord été exploitées afin d'obtenir avec un agent chélatant unique et rigoureusement sélectionné, l'acide 2-hydroxy-2-methylbutyrique (HMBA), la sélectivité intra période nécessaire à leur séparation complète par ITP. Basées sur des modèles théoriques existants, des études complémentaires, notamment des paramètres influençant la résolution, ont permis l'amélioration des performances globales du système ainsi que son dimensionnement. Pour réduire drastiquement le volume de déchets liquides secondaires (solutions de rinçage) et la manipulation de matériaux et de matériels radioactifs, le protocole a été implanté sur un microsystème polymérique jetable en COC, spécialement développé pour cette application. Ce microsystème a ensuite été couplé à un spectromètre de masse a multi collection et source à plasma à couplage inductif pour mesurer les rapports isotopiques

Dreiwertige Actinide (An(III)) und Lanthanide (Ln(III)) stellen im Falle ihrer Inkorporation eine ernste Gefahr für die Gesundheit des Menschen dar. An(III) sind künstlich erzeugte, stark radioaktive Elemente, die insbesondere bei der nuklearen Energiegewinnung in Kernkraftwerken entstehen. Durch Störfälle oder nicht fachgerechte Lagerung radioaktiven Abfalls können sie in die Umwelt und die Nahrungskette des Menschen gelangen. Ln(III) sind hingegen nicht radioaktive Elemente, die natürlicherweise vorkommen und für vielfältige Anwendungen in Technik und Medizin abgebaut werden. Folglich kann der Mensch sowohl mit An(III) als auch Ln(III) in Kontakt kommen bzw. sie inkorporieren. Es ist daher von enormer Wichtigkeit, das Verhalten dieser Elemente im menschlichen Körper aufzuklären. Während makroskopische Vorgänge wie Verteilung, Anreicherung und Ausscheidung bereits sehr gut untersucht sind, ist das Wissen hinsichtlich der chemischen Bindungsform (Speziation) von An(III) und Ln(III) in Körperflüssigkeiten noch sehr lückenhaft. In der vorliegenden Arbeit wurde daher erstmals die chemische Bindungsform von Cm(III) und Eu(III) in natürlichem menschlichem Urin (in vitro) spektroskopisch aufgeklärt und die gebildeten Komplexe identifiziert. Hierzu wurden auch grundlegende Untersuchungen zur Komplexierung von Cm(III) und Eu(III) in synthetischem Modellurin sowie mit den urinrelevanten organischen Modellliganden Harnstoff, Alanin, Phenylalanin, Threonin und Citrat durchgeführt und die noch unbekannten Komplexbildungskonstanten bestimmt. Abschließend wurden alle experimentellen Ergebnisse mit Literaturdaten und Vorherberechnungen mittels thermodynamischer Modellierung verglichen. Auf Grund der hervorragenden Lumineszenzeigenschaften von Cm(III) und Eu(III) konnte insbesondere auch die Eignung der zeitaufgelösten laserinduzierten Fluoreszenzspektroskopie (TRLFS) als Methode zur Untersuchung dieser Metallionen in unbehandelten, komplexen biologischen Flüssigkeiten demonstriert werden. Die Ergebnisse dieser Arbeit liefern damit neue Erkenntnisse zu den biochemischen Reaktionen von An(III) und Ln(III) in Körperflüssigkeiten auf molekularer Ebene und tragen zu einem besseren Verständnis der bekannten, makroskopischen Effekte dieser Elemente bei. Darüber hinaus sind sie die Grundlage weiterführender in-vivo-Untersuchungen. / In case of incorporation, trivalent actinides (An(III)) and lanthanides (Ln(III)) pose a serious health risk to humans. An(III) are artificial, highly radioactive elements which are mainly produced during the nuclear fuel cycle in nuclear power plants. Via hazardous accidents or nonprofessional storage of radioactive waste, they can be released in the environment and enter the human food chain. In contrast, Ln(III) are nonradioactive, naturally occurring elements with multiple applications in technique and medicine. Consequently it is possible that humans get in contact and incorporate both, An(III) and Ln(III). Therefore, it is of particular importance to elucidate the behaviour of these elements in the human body. While macroscopic processes such as distribution, accumulation and excretion are studied quite well, knowledge about the chemical binding form (speciation) of An(III) and Ln(III) in various body fluids is still sparse. In the present work, for the first time, the speciation of Cm(III) and Eu(III) in natural human urine (in vitro) has been investigated spectroscopically and the formed complex identified. For this purpose, also basic investigations on the complex formation of Cm(III) and Eu(III) in synthetic model urine as well as with the urinary relevant, organic model ligands urea, alanine, phenylalanine, threonine and citrate have been performed and the previously unknown complex stability constants determined. Finally, all experimental results were compared to literature data and predictions calculated by thermodynamic modelling. Since both, Cm(III) and Eu(III), exhibit unique luminescence properties, particularly the suitability of time-resolved laser-induced fluorescence spectroscopy (TRLFS) could be demonstrated as a method to investigate these metal ions in untreated, complex biofluids. The results of this work provide new scientific findings on the biochemical reactions of An(III) and Ln(III) in human body fluids on a molecular scale and contribute to a better understanding of the known macroscopic effects of these elements. Furthermore, they are the basis of subsequent in vivo investigations.

La fluorescence en temps résolu est une méthode d'analyse spectrophotométrique avancée permettant la sélection des photons émis par luminescence sur un critère temporel. Il est ainsi possible, et cela même dans des milieux complexes et pollués issu de l'industrie, de faire émerger sélectivement le signal d'espèces luminescentes présentant des durées de vie de luminescence relativement grandes.Ce type d'analyse spectrale est particulièrement adapté à la détection de trace d'éléments lanthanides. Chacun des éléments de la série présente en effet des propriétés luminescentes uniques bien que largement fonction de la nature des ligands qui les entourent. Les travaux de thèse présentés dans ce manuscrit utilisent avantageusement la constatation précédente. Deux technologies ont étés mise sur pied et/ou optimisées pour permettre un transfert vers des domaines industriels aux cahiers des charges bien définis.Ainsi dans le domaine de la lutte anti-contrefaçon l'ajout de marqueurs luminescents à temps résolu à base de lanthanide rend possible la surveillance de l'origine et du devenir de divers produits industriels.Dans le domaine pétrolier l'analyse des effluents à l'aide de sondes luminescentes à base de lanthanide permet de quantifier le taux résiduel de plusieurs classes d'additifs chimiques et permet d'optimiser la sécurité, la rentabilité et l'impact écologique du processus d'extraction.Dernièrement un prototype de spectrofluorimètre résolu en temps adapté à un usage industriel a été mis au point pour permettre un transfert technologique du laboratoire vers le milieu industriel / Time-resolved fluorescence is an advanced spectrophotometric analysis method which allows the selection of emitted luminescent photons on a time-based parameters. It is possible to extract the signal of long-lived luminescent species even in complex and polluted matrix from the industry. This type of analysis is especially fitted for the detection of lanthanide ions. During this thesis two technologies based on time-resolved analysis were designed to answer specific industrial problematics. The first one yields the residual concentration of chemical additives used during oil and gas extraction. The second one aims at protecting crude oils and refined fuels from counterfeiting. They both rely on the use of lanthanide complex and the measurement of their luminescent properties. A prototype of time-resolved spectrofluorimeter was also built to transfer the technologies from the laboratory to the industrial world

Chapter 1: Introduction to the luminescent properties of lanthanides Luminescence properties of trivalent lanthanides have been explored extensively over the past few decades owing to their unique properties. Lanthanides emission is known to be due to intra-configurational f-f transitions. Because the partially filled 4f shell is well shielded from its 26 environment by the closed 5sand 5pshells, the ligands in the first and second coordination sphere perturb the electronic configurations of the trivalent lanthanide ions only to a very limited extent. This leads to interesting properties such as long lifetimes, sharp line-like emissions etc. which in turn make lanthanides very attractive choice for commercial optical applications. Despite this, the scope of applications remained limited because of the low molar extinction coefficient values of the forbidden lanthanide f-f transitions. However, this problem has been successfully addressed by complexing the lanthanide ion with suitable ligands which can sensitize it resulting in a significant increase in the emission intensity (so called “antenna effect”). The strategy worked very well and resulted in widespread applications of lanthanides form biology to optoelectronics. This chapter discusses elementary ideas regarding the mechanism of sensitization and relevant examples that traces various applications of such lanthanide complexes from the current literature. Chapter 2: A self-assembled Europium Cholate hydrogel: a novel approach towards lanthanide sensitization Luminescent lanthanides can be of great value in a number of possible applications but their scope is limited by their intrinsic low molar absorptivities. Though this problem can be circumvented by complexing the lanthanide ion with suitable chelating ligands to improve the luminescence properties drastically, the design of such systems often involves meticulous planning and laborious synthetic steps to obtain a ligand suitable for the job. It is therefore desirable to have a simpler version of a sensitizing system that does not require the complexities of a chelating ligand but can sensitize trivalent lanthanides with comparable efficiency. It was observed in our group that divalent metal ions (Ni2+, Zn2+, Cu2+, Coetc.) form hydrogels on addition of sodium cholate. We extended to obtain hydrogels of trivalent lanthanides. Furthermore, when the gel was doped with pyrene, a ten-fold increase in the intensity of Eu(III) emission was observed (Fig 2). Thus we established a unique way to sensitize lanthanides in a hydrogel media by non-coordinating chromophores. The approach was completely modular in nature and avoids any laborious synthesis. We also tried other derivatives of pyrene as sensitizers and found that 1-pyreneboronic acid also caused similar sensitization of Eu(III). Fig 2. (a) Schematic representation of the sensitization process (the arrangement of molecules in the gel fiber is arbitrary). Eu-cholate (5 mM/15 mM) gel (a) normal light and (b) 354 nm UV excitation in the presence of 6 μM pyrene Further studies revealed, that 2,3-dihydroxynapthalene (DHN) can sensitize Tb(III) in a similar hydrogel. We also demonstrated Tb(III) to Eu(III) energy transfer process occurring in the gel when doped with DHN. This allowed us to achieve a hydrogel system with tunable luminescence properties (by varying relative ratios of Tb(III) and Eu(III) ). When the effect of divalent metal ions on such energy transfer processes were explored, it was observed that the luminescence from the composite gel of Tb(III)/ Eu(III) is tunable by Zn(II) and through proper manipulation of concentrations one can obtain white light emitting gel (Fig 3). Fig 3. Effect of Zn(II) (from left to right 0 mM, 2.8 mM, 11.3 mM) on Tb3+ (4.5 mM)/Eu3+ (0.11mM)/ sodium cholate (13.6 mM) gels. b) Tb/Eu/Zn-cholate gel (Tb3+ (4.4 mM), Eu3+ (0.11 mM), Zn2+ (7.4 mM), NaC (13.6 mM, DHN 0.2 mM) under 365 nm UV lamp (c) CIE 1931 diagram depicting the luminescence as white (black spot). Chapter 3. A “Pro-Sensitizer” based Sensing of Enzymes using Tb(III) Luminescence in a Hydrogel matrix This chapter descirbes design and realisation of a sensor system based on Tb(III) luminescnece for the detection of enzymes. The idea involved synthesizing a covalently modified DHN molecule by attaching appropriate enzyme cleavable units. We coined the term “pro-sensitizer”to describe the modified molecule which would not sensitize Tb(III) in the gel matrix but when proper enzymes are applied the free form of DHN would be released triggering a luminescence response from Tb(III). This would enable us to monitor the acitivities of the particular enzyme by examining the luminescence intensity enhancement with time (Fig 4) Fig 4. A “pro-sensitizer” based approach to detect different types of enzymes in a hydrogel matrix through Tb(III) luminescence. We applied the idea to develop a novel luminogenic gel probe for inexpensive and rapid detection of three different hydrolases, lipase, β–glucosidase and α-chymotrypsin. The corresponding “pro-sensitizer”for each enzyme were synthesized (Fig 5).The sensing technique depends on the gel matrix to provide the nessesary platform for lanthanide sensitization. Thereofore, it enjoys an edge over the contemporary techniques that typically involve specially designed and synthesized multidentate chelating ligands for this purpose. We also determined important kinetic parameters of all the enzymes, thus enabling us to have a better insight into the activity of the enzymes in the hydrogel matrix. Fig 4. Pro-sensitizers molecules for (1) lipase, (2) β-glucosidase and (3)α-chymotrypsin Chapter 4. A novel approach towards templated synthesis of lanthanide trifluoride nanoparticles Nanomaterials with excellent optical properties have been of special interest. Lanthanide derived nanoparticles, owing to their unique physical properties, provide an excellent choice for applications such as biolabels, lasers, optical amplifiers, and optical-display phosphors. Several types of lanthanide nanoparticles or nanocrystals are reported in the literature such as Nd2O3, Eu2O3, Gd2O3, Tb2O3, and Y2O3. Among them lanthanide fluoride nanoparticles have emerged as the best choice because of their low phonon energy, and thus minimum quenching of emissive Lnions thereby allowing maximum efficiency for several optical applications. In previous literature precedence, LnF3 nanoparticles were typically synthesized following conventional approaches which necessitate use of high temperatures, high pressures (hydrothermal techniques) and capping ligands. In this chapter, we demonstrated a simpler synthesis of LnF3 nanoparticles at ambient temperatures without the requirement of added capping agents. The room temperature synthesis of LnF3 was unprecedented and was achieved simply by diffusing NaF solution through the hydrogels of corresponding Ln-cholate gels. The nanoparticles were characterized by transmission electron microscopy (TEM) and by powder XRD analysis which established the presence of very small (3-4 nm) nanoparticles mono-dispersed uniformly over the the gel matrix (Fig 6). The LnF3 containing xerogels of Tb(III) and Eu(III) cholate gels were also shown to be highly emissive. Fig 6. HRTEM images of a) TbF3, b) GdF3, c) NdF3 and d) DyF3 in their corresponding gel media.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A theoretical study of the interactions between the 4f electrons in lanthanide ions (Ln3 +) with the chemical environment was made using crystal field theory. The main effects were studied: change in position of the berycentre of the energy levels of the free ion, maximum splitting of the J level and contribution to 5D0-7F0 transition of Eu3+ ion. Use of second-order correction to the wave functions allow a better understanding the relationship between the maximum splitting 7F1 Eu3+ ion and the position of its berycentre. The dependence between the intensity of the 5D0-7F0 transition with its position was also demonstrated using the linear part of the crystal field. This study was done based on symmetry properties of the Hamiltonian of the free ion and crystal field. The predicted position of the berycentre and the maximum splitting of the 7F1 level are in good agreement with the experimental results. The equations for the 5D0-7F0 transition satisfactorily reproduced the experimental data and can be used for the Sm2+ ion. / Um estudo teórico das interações entre os elétrons 4f de íons lantanídeos (Ln3+) íon com o meio químico foi feito usando a teoria de campo cristalino. Os principais efeitos estudados foram: mudança na posição do baricentro dos níveis de energia do íon livre, desdobramento máximo do nível J e contribuição para transição 5D0-7F0 do íon Eu3+. Usar a correção de segunda ordem para as funções de onda permitiu entender melhor como é a relação entre o desdobramento máximo do 7F1 do íon Eu3+ e a posição de seu baricentro. A dependência entre intensidade da transição 5D0-7F0 com a sua posição também foi demonstrada usando a parte linear do campo cristalino. Este estudo foi feito baseado em propriedades de simetria do hamiltoniano do íon livre e do campo cristalino. A previsão da posição do baricentro e do desdobramento do nível 7F1 estão em bom acordo com os resultados experimentais. As equações obtidas para a transição 5D0-7F0 reproduziram satisfatoriamente os resultados experimentais e podem ser usadas para o íon Sm2+.

In this work siloxane-polymethyl methacrylate (PMMA) hybrid materials were synthesized and doped with Eu (III) from solid europium chloride, solid europium (III) nitrate, europium chloride (III) in alcoholic solution and 3-aminopyrazine-2-carboxylate of lanthanum and europium complex. The hybrid was prepared from methyl methacrylate (MMA) and 3-methacryloxy-propyl-trimethoxysilane (MPTS), using benzoyl peroxide (BPO) as polymerization initiator. The use of the sol-gel method by acid catalysis allowed to obtain pure solid materials and doped with europium different sources with amorphous characteristics, as evidenced by the X-ray diffraction powderdata. The insertion of the europium complex in the polycrystalline matrix did not changethe structural characteristics of the samples. It was observed that the materials doped with europium in solution, showed greater adsorbed amounts of solvents and structural features that changethe spectroscopic properties. The samples containing solid salts showed similar structural features. It was observed that the average life time of the radioactive emissions increase with the heat treatment, indicating that the temperature reduces the number of suppressor luminescence groups in the coordinationenvironment oflanthanides ion and the character non monoexponentialof the decay is indicative of the presence different coordination environments. In the 29Si NMR measurementsfor samples containing alcoholic solution of europium chloride are observed monomer (RSi(OSi)(OH)2), diimeric(R-Si(OSi)2(OH)) and fully condensed (RSi(OSi)3)species,having a polycondensationdegree up to 78% . The materialsdoped with europium complex show strong luminescence, except tosamples treated at 200 ° C, which is indicative of thermal degradation of the coordination complex. It was observed that presence of solvent changedthermal stability, different heat treatments and europium sources exerted strong influence on the coordination environment of the Eu (III) ions in the organic -inorganic hybrid materials. / Neste trabalho materiais híbridos Siloxano-Polimetacrilato de metila (PMMA) foram sintetizados e dopados com íons Eu(III) provenientes de cloreto e nitrato de európio (III) sólidos, cloreto de európio (III) em solução alcoólica e complexo 3-aminopirazina-2-Carboxílato de lantânio e európio. O hibrido foi preparado a partir dometacrilato de metila (MMA) e do 3-metacriloxi-propil-trimetoxisilano (MPTS), utilizando-se como agente inicializador de polimerização o peróxido de benzoila (BPO). A utilização dametodologia de síntese sol-gel por catálise ácida possibilitou a obtenção de materiais sólidos puros e dopados com diferentes fontes de európio, com características amorfas, como ficou evidente pelos dados de difração de raios X de pó. A inserção de complexo de európiopolicristalino na matriz não alterou as características estruturais da amostra.Observou-se que os materiais que foram dopados com európio em solução, apresentaram maior quantidade de solventes adsorvidos e características estruturais que alteraram as suas propriedades espectroscópicas. As amostras dopadas com sais sólidos apresentaram características estruturais semelhantes. Observou-se que os tempos de vida médios das emissões radiativas aumentam com o tratamento térmico, o que indica que o tratamentoreduz o número de grupos supressores de luminescência no ambiente de coordenação do íon lantanídeo e o caráter não monoexponencial do decaimento é indicativo da presença de diferentes ambientes de coordenação. Pelo RMN do 29Si para as amostras dopadas com solução alcoólica de cloreto de európio são observadas espécies monoméricas(R-Si(OSi)(OH)2), diméricas(R-Si(OSi)2(OH)) e totalmente condensadas(R-Si(OSi)3) com um grau de policondensação de até 78%. Os materiais dopados com o complexo apresentam forte luminescência, exceto as amostras tratadas a 200°C, o que é indicativo da degradação térmica do complexo de coordenação. Observou-se que a presença de solvente alterou a estabilidade térmica das amostras, e que a diferentes tratamentos térmicos e a dopagem com diferentes fontes de európio influenciaram sensivelmente o ambiente de coordenação dos íons Eu(III) nos materiais híbridos orgânico-inorgânicos.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / A new approach to describe the crystal field interaction in compounds that contains trivalent lanthanide ions is presented. It is considered the electrostatic balance of the optically active site, the effective charge of the central ion and the sign of crystal field parameters (CCP) as determinant factors in the crystal field interaction. The method of the first equivalent neighbours (MENN) was reformulated, and improvements in predicting the CCP and energy levels 7FJ of Eu3+ could be realized. Moreover, it was possible to predict the lanthanide-nearest neighbour interaction of load factors (Ln-NN), the maximum coverage of the wave functions of the interacting ions and energy levels levels structure of the 7FJ of Eu3+. The physically acceptable limits are designed to load factors and the maximum overlap of the wave functions of the interacting ions. The compounds studied have high symmetry and exhibit a first neighbourhood consisting of oxygen ions, fluorine or chlorine. The use of secular determinants solutions of the energy matrices served as an excellent theoretical framework for the development of the method, which is applied based on the simple overlap model (SOM). This allowed the description of the interaction of the crystalline field by a nonparametric method and simple application. In addition, it was predicted the wave functions overlap factor of the interacting ions, the total effective bonding charge of Eu3+, and the relationships and trends of the crystal field interaction with the chemical species of the NN and the type of Ln that makes up the main host matrix. Finally, it was possible to remodulate the MENN at a more theoretical method by using theoretical data. The results served to confirm the efficiency and accuracy of MENN in describing the interaction of the crystal field on systems containing trivalent lanthanide ions. / Uma nova abordagem na descrição da interação do campo cristalino em compostos contendo íons lantanídeos trivalentes é apresentada. São considerados o equilíbrio eletrostático do sítio opticamente ativo, a carga efetiva do íon central e o sinal dos parâmetros de campo cristalino (PCC) como fatores determinantes na descrição da interação de campo cristalino. O método dos primeiros vizinhos equivalentes (MENN) foi reformulado, e assim melhorias na previsão dos PCC e dos níveis de energia 7FJ do Eu3+ puderam ser realizadas. Além disso, foi possível prever fatores de carga de interação lantanídeo-primeiro vizinho (Ln-PV), o recobrimento máximo das funções de onda dos íons interagentes e estrutura dos níveis níveis de energia 7FJ do Eu3+. Foram estabelecidos limites fisicamente aceitáveis para os fatores de carga e para o recobrimento máximo das funções de onda dos íons interagentes. Os compostos estudados possuem alta simetria e apresentam uma primeira vizinhança composta por íons de oxigênio, flúor ou cloro. A utilização das soluções dos determinantes seculares das matrizes energéticas serviram como um excelente aporte teórico para o desenvolvimento do método, o qual é aplicado tendo por base o modelo de recobrimento simples (SOM). Isto permitiu a descrição da interação do campo cristalino por um método não paramétrico e de simples aplicação. Além disso, foi realizada a previsão do fator de recobrimento das funções de onda dos íons interagentes, carga efetiva total de ligação do Eu3+, e as relações e tendências da interação do campo cristalino com a espécie química dos PV, e o tipo de Ln que compõe a matriz hospedeira principal. Por fim, foi possível tornar o MENN um método mais teórico através da utilização de dados teóricos. Os resultados obtidos serviram para confirmar a eficiência e precisão do MENN na descrição da interação do campo cristalino em sistemas contendo íons lantanídeos trivalentes.