Une fermeture de sous-couche à N=70 dans le ¹¹⁰Zr a longtemps été considérée comme une explication possible du désaccord entre la théorie et les abondances observées des éléments lourds près de la masse 130 résultant du processus de capture rapide des neutrons (processus r). Le processus r n’est pas bien compris en partie à cause des incertitudes relatives aux mécanismes d'évolution de la structure en couches des noyaux riches en neutrons. La fermeture de sous-couche dans le ¹¹⁰Zr, bien qu’improbable, pourrait résulter d’une symétrie tétraédrique ou sphérique. Ces symétries laissent des indications distinctes sur la structure des niveaux de basse énergie et leur effet peut donc être détecté par une simple mesure de spectroscopie. Le système MINOS a été employé à l'installation de faisceaux d'isotopes radioactifs (RIBF) de RIKEN au Japon pour effectuer la première spectroscopie du ¹¹⁰Zr. MINOS, développé au CEA-IRFU, combine une cible de protons épaisse avec un dispositif de reconstruction de vertex de réaction pour permettre une spectroscopie à haute résolution des noyaux rares. Les états de basse énergie dans le ¹¹⁰Zr ont été peuplés par arrachage des protons de la cible MINOS, et les rayons gamma de désexcitation ont été détectés avec l'ensemble de scintillateurs DALI2. Les résultats sont compatibles avec un noyau bien déformé. Aucune preuve n’est obtenue pour une fermeture de sous-couche à N = 70 ni en faveur de la symétrie tétraédrique. Une étude complémentaire explore les sections efficaces inclusives pour les réactions (p,2p) et (p,pn) avec les noyaux riches en neutrons. Environ 60 sections efficaces inclusives ont été mesuré pour l’arrachage d'un nucléon sur la cible MINOS. La systématique (p,2p) montre une augmentation de la section efficace pour les noyaux fils de Z impair, ce qui révèle l'importance des corrélations d'appariement. Les sections (p,pn) sont plus grandes que les sections efficaces (p,2p), d'environ un facteur 10, distribuées aléatoirement autour de 60 mb. La comparaison avec les modèles semi-classiques suggère que ces deux systématiques peuvent être expliquées par le rôle important des corrélations d'appariement dans les systématiques de réactions directes induites par les noyaux exotiques. Enfin, des simulations électrostatiques ont été menés pour optimiser la cage de champ électrique de la chambre de projection temporelle MINOS, en vue d'une future application pour un nouveau programme de physique au CERN appelé PUMA. / A predicted N=70 subshell closure in ¹¹⁰Zr has long been considered a potential explanation for the disagreement between theory and observed abundances of the heavy elements near mass 130 resulting from the rapid neutron capture process (r-process). The r-process is not well understood, due in part to the uncertainties of the neutron-rich structure evolution mechanisms. A subshell closure in ¹¹⁰Zr, though unlikely, could result from either a tetrahedral or spherical symmetry. Each of these symmetries leaves distinct fingerprints on the low lying level structure, and thus can be discerned with a simple spectroscopy measurement. The MINOS system has been used at the Radioactive Isotope Beam Factory of RIKEN in Japan to perform the first spectroscopy of ¹¹⁰Zr. MINOS, developed at CEA-IRFU, combines a thick proton target with a vertex tracker to allow high resolution spectroscopy of rare nuclei. Low lying states in ¹¹⁰Zr were populated via proton removal on the MI- NOS target, and deexcitation gamma rays detected with the DALI2 scintillator array. Results are consistent with a well deformed nucleus. No evidence is found for a subshell closure at N=70 nor tetrahedral symmetry. A complementary study explores inclusive cross sections for (p,2p) and (p,pn) reactions with neutron rich nuclei. Approximately 60 inclusive cross sections have been measured for single nucleon removal on the MINOS target. The (p,2p) systematics reveal an enhanced cross section to odd-Z daughter nuclei, pointing to the importance of pairing correlations. The (p,pn) cross sections are approximately a factor of 10 larger than the (p,2p) cross sections, randomly distributed around 60 mb. Comparison with semi-classical models suggest that both these systematics can be explained by the important role of pairing correlations in direct reaction systematics for exotic nuclei. Finally, the electric field cage of the MINOS time projection chamber is optimized with electrostatic simulations in view of a future application as a pion tracker for antiproton-nucleus collisions in a new physics program at CERN called PUMA.

With the availability of high reflectivity multilayer mirrors and zone plate lenses, the EUV region (5nm - 40nm) of the electromagnetic spectrum is currently being explored for applications of nanoscale printing and imaging. Advances made in this area have consequences for many areas of science. Research for producing a compact, bright EUV source for laboratory use has gained momentum in recent years. For this study, EUV radiation is produced by irradiating target materials using a focused laser beam. Focused laser beam ionizes the target to create a hot, dense, pulsed plasma source, where emission is a result of the relaxation of excited levels. Spectroscopy is used as the main diagnostic to obtain the spectral signature of the plasma. Spectral characteristics are used to deduce the physical state of plasma, thus enabling the tuning of laser irradiance conditions to maximize the needed emission bandwidth. Various target materials are studied, as well as different target geometries, with spectroscopy below 200 nm on pulsed micro-plasmas being a particularly daunting task. Total range spectroscopy from 1 nm to greater than 1 micron is completed for tin-doped spherical droplet plasma source. Reliable plasma diagnostics require both accurate measurements and solid theoretical support in order to interpret the experimental results. Using existing 1D-hydrocode, temperature and density characteristics of the expanding plasma is simulated for any set of experimental conditions. Existing atomic codes written for calculating one-electron radial wavefunctions with LS-coupling scheme via Hartree-Fock method is used in order to gain details of the ion stages, populations, transitions, etc, contributing to the spectral data.

A conjugação por polietilenoglicol (PEG) mascara a superfície das proteínas e aumenta o tamanho molecular do polipeptídio, reduzindo assim sua ultrafiltragem renal, impedindo a aproximação de células processadoras de antígenos ou anticorpos e reduzindo a degradação por enzimas proteolíticas. O PEG transfere para as moléculas suas propriedades físico-químicas e, conseqüentemente, modifica também a biodistribuição e a solubilidade de drogas peptídicas e não peptídicas. As soluções de proteínas são facilmente desnaturadas (muitas vezes irreversivelmente) pelo aparecimento de numerosos eventos que podem afetar a estabilidade das soluções, tais como: aquecimento, agitação, congelamento, mudanças no pH e exposição a interfaces ou agentes desnaturantes, resultando geralmente na perda da eficácia clínica e aumento do risco de efeitos colaterais adversos. A solução prática para o dilema da estabilidade da proteína é a remoção da água. A liofilização é o método mais comumente utilizado para a preparação de proteínas desidratadas, as quais, teoricamente, devem apresentar uma estabilidade adequada por um longo período de armazenagem em temperaturas ambientes. A proteína utilizada neste estudo foi a albumina sérica bovina (BSA), amplamente estudada no campo da bioquímica. Através da espectroscopia Raman associada com análise térmica por DSC, análise colorimétrica, e a determinação do teor de umidade, verificou-se que o congelamento rápido (30 °C/min.) favoreceu a manutenção da estrutura conformacional da proteína após a liofilização, porém aumentou o tempo de secagem primária em sete horas em relação ao congelamento lento (2,5 °C/min.). Após a modificação da albumina bovina por reação com o metoxi-PEG verificou-se que a BSA-PEG (1:0,25) apresentou um menor grau de alteração estrutural e conseqüentemente uma menor variação das características físico-químicas, além de otimizar as condições de liofilização e armazenamento da proteína quando comparada com a BSA-PEG (1:0,5) . / PEG conjugation masks the proteins surface and increases the molecular size of the polypeptide, thus reducing its renal ultrafiltration, preventing the approach of antibodies or antigen processing cells and reducing the degradation by proteolytic enzymes. The PEG conveys to molecules its physico-chemical properties and therefore modifies also biodistribution and solubility of peptide and non-peptide drugs. This property opens new techniques in biocatalysis and in pharmaceutical technology where many insoluble drugs are solubilized by PEG conjugation and thus more easily administered. Aqueous protein solutions are readily denatured (often irreversibly) by numerous stresses arising in solution, e.g., heating, agitation, freezing, pH changes, and exposure to interfaces or denaturants, usually resulting in lost of clinical efficacy and increase the risk of adverse side effects. Even if its physical stability is maintained, a protein can be degraded by chemical reactions (e.g., hydrolysis and deamidation), many of which are mediated by water. The practical solution to the protein stability dilemma is to remove the water. Lyophilization is most commonly used to prepare dehydrated proteins, which, theorecally, should have the desired long-term stability at ambient temperatures. The protein used in this study was the bovine serum albumin (BSA), largely studied in the biochemical field. Through Raman spectroscopy associated with thermal analysis using DSC, Colorimetric analysis and the determination of water content It was observed that the fast freezing (30 °C/min.) favored the maintenance of the conformational structure in the protein after lyophilization, however increased the primary drying in seven hours with regard to the slow freezing (2,5 °C/min.). After the modification of bovine serum albumin with methoxy-PEG it was observed that the BSA-PEG (1:0,25) showed a lower degree of structural alterations and consequently a lower variation on the physical-chemical characteristics, moreover optimized the conditions during the lyophilization process and storage of the protein when it was compared to BSA-PEG (1:0,5).

A conjugação por polietilenoglicol (PEG) mascara a superfície das proteínas e aumenta o tamanho molecular do polipeptídio, reduzindo assim sua ultrafiltragem renal, impedindo a aproximação de células processadoras de antígenos ou anticorpos e reduzindo a degradação por enzimas proteolíticas. O PEG transfere para as moléculas suas propriedades físico-químicas e, conseqüentemente, modifica também a biodistribuição e a solubilidade de drogas peptídicas e não peptídicas. As soluções de proteínas são facilmente desnaturadas (muitas vezes irreversivelmente) pelo aparecimento de numerosos eventos que podem afetar a estabilidade das soluções, tais como: aquecimento, agitação, congelamento, mudanças no pH e exposição a interfaces ou agentes desnaturantes, resultando geralmente na perda da eficácia clínica e aumento do risco de efeitos colaterais adversos. A solução prática para o dilema da estabilidade da proteína é a remoção da água. A liofilização é o método mais comumente utilizado para a preparação de proteínas desidratadas, as quais, teoricamente, devem apresentar uma estabilidade adequada por um longo período de armazenagem em temperaturas ambientes. A proteína utilizada neste estudo foi a albumina sérica bovina (BSA), amplamente estudada no campo da bioquímica. Através da espectroscopia Raman associada com análise térmica por DSC, análise colorimétrica, e a determinação do teor de umidade, verificou-se que o congelamento rápido (30 °C/min.) favoreceu a manutenção da estrutura conformacional da proteína após a liofilização, porém aumentou o tempo de secagem primária em sete horas em relação ao congelamento lento (2,5 °C/min.). Após a modificação da albumina bovina por reação com o metoxi-PEG verificou-se que a BSA-PEG (1:0,25) apresentou um menor grau de alteração estrutural e conseqüentemente uma menor variação das características físico-químicas, além de otimizar as condições de liofilização e armazenamento da proteína quando comparada com a BSA-PEG (1:0,5) . / PEG conjugation masks the proteins surface and increases the molecular size of the polypeptide, thus reducing its renal ultrafiltration, preventing the approach of antibodies or antigen processing cells and reducing the degradation by proteolytic enzymes. The PEG conveys to molecules its physico-chemical properties and therefore modifies also biodistribution and solubility of peptide and non-peptide drugs. This property opens new techniques in biocatalysis and in pharmaceutical technology where many insoluble drugs are solubilized by PEG conjugation and thus more easily administered. Aqueous protein solutions are readily denatured (often irreversibly) by numerous stresses arising in solution, e.g., heating, agitation, freezing, pH changes, and exposure to interfaces or denaturants, usually resulting in lost of clinical efficacy and increase the risk of adverse side effects. Even if its physical stability is maintained, a protein can be degraded by chemical reactions (e.g., hydrolysis and deamidation), many of which are mediated by water. The practical solution to the protein stability dilemma is to remove the water. Lyophilization is most commonly used to prepare dehydrated proteins, which, theorecally, should have the desired long-term stability at ambient temperatures. The protein used in this study was the bovine serum albumin (BSA), largely studied in the biochemical field. Through Raman spectroscopy associated with thermal analysis using DSC, Colorimetric analysis and the determination of water content It was observed that the fast freezing (30 °C/min.) favored the maintenance of the conformational structure in the protein after lyophilization, however increased the primary drying in seven hours with regard to the slow freezing (2,5 °C/min.). After the modification of bovine serum albumin with methoxy-PEG it was observed that the BSA-PEG (1:0,25) showed a lower degree of structural alterations and consequently a lower variation on the physical-chemical characteristics, moreover optimized the conditions during the lyophilization process and storage of the protein when it was compared to BSA-PEG (1:0,5).

The present thesis is devoted to two major atmospheric species – water and oxygen. The absorption spectrum of the 1Delta band of six oxygen isotopologues near was recorded by very high sensitivity CW-CRDS at room temperature and at 80 K. The magnetic dipole-allowed (0-0) band is observed for 16O2, 16O18O, 16O17O, 17O18O, 18O2 and 17O2. The first laboratory detection of extremely weak quadrupole transitions in the (0-0) band of 18O2, 16O17O, 17O2 is reported together with the (1-1) hot band of 16O2, 18O2, 16O17O and 17O2. The partly resolved hyperfine structure of the 16O17O, 17O18O, 17O2 transitions is analysed. These measurements combined with microwave and Raman data available in the literature led to the determination of the best to date spectroscopic constants for the six oxygen isotopologues, including the 17O hyperfine coupling parameters for the 1Delta state. The high resolution absorption spectra of water isotopologues (D216O, HD16O and H218O) were recorded by ICLAS and FTS in the 8800–14100 cm-1 region. The spectrum analysis based on high accuracy variational calculations provided a considerable amount of new energy levels for each of the isotopologues under consideration. The experimental energy levels derived in this study and available in the literature allowed calculating the line positions at the level of experimental accuracy in the 6100–15200 cm-1 region that extends much further the range of the present recordings. / Cette thèse est consacrée à deux espèces atmosphériques majeures: la vapeur d'eau et l'oxygène. Le spectre d'absorption de la bande 1Delta des six isotopologues de l'oxygène vers 1.27 micron a été enregistré à température ambiante et à 80 K par la technique CW-CRDS de très haute sensibilité. La bande (0-0) permise par le dipôle magnétique est observée pour les espèces 16O2, 16O18O, 16O17O, 17O18O, 18O2 et 17O2. La sensibilité expérimentale atteinte a permis de détecter pour la première fois au laboratoire (i) des transitions quadrupolaires électriques extrêmement faibles dans la bande (0-0) de 18O2, 16O17O et 17O2, (ii) la bande chaude (1-1) de 16O2, 18O2, 16O17O et 17O2 (iii) la structure hyperfine des transitions de 16O17O, 17O18O et 17O2. Ces mesures combinées avec des données micro-ondes et Raman disponibles dans la littérature ont permis de déterminer les meilleures constantes spectroscopiques à ce jour, y compris les paramètres de couplage hyperfin de 17O pour l'état 1Delta des six isotopologues de l'oxygène. Les spectres d'absorption à très haute résolution des isotopologues D216O, HD16O et H218O de la vapeur d'eau ont été enregistrés par ICLAS et FTS entre 8800 et 14100 cm-1. L'analyse du spectre basée sur les calculs variationnels de haute précision a fourni une quantité importante de nouveaux niveaux d'énergie pour chacun des isotopologues considérés. Les niveaux d'énergie expérimentaux obtenus dans cette étude et disponibles dans la littérature ont permis de calculer des positions de raies au niveau de la précision expérimentale dans la gamme 6100-15200 cm-1 qui s'étend bien au-delà de la gamme des enregistrements présents.

In this thesis, two recently discovered polymorphs of LiFeSO4F, adopting a tavorite- and triplite-type structure, were investigated as potential candidates for use as cathode materials in Li-ion batteries. The studies aimed at enriching the fundamental understanding of the synthetic preparations, structural properties, and electrochemical functionality of these materials. By in situ synchrotron X-ray diffraction (XRD), the formation mechanism of the tavorite-type LiFeSO4F was followed starting from two different sets of precursors, FeSO4∙H2O + LiF, and Li2SO4 + FeF2. The results indicated that the formation of LiFeSO4F is possible only through the structurally related FeSO4∙H2O, in line with the generally recognized topotactic reaction mechanism. Moreover, an in-house solvothermal preparation of this polymorph was optimized with the combined use of XRD and Mössbauer spectroscopy (MS) to render phase pure and well-ordered samples. Additionally, the triplite-type LiFeSO4F was prepared using a facile high-energy ball milling procedure. The electrochemical performance of as-prepared tavorite LiFeSO4F was found to be severely restricted due to residual traces of the reaction medium (tetraethylene glycol (TEG)) on the surface of the synthesized particles. A significantly enhanced performance could be achieved by removing the TEG residues by thorough washing, and a subsequent application of an electronically conducting surface coating of p-doped PEDOT. The conducting polymer layer assisted the formation of a percolating network for efficient electron transport throughout the electrode, resulting in optimal redox behavior with low polarization and high capacity. In the preparation of cast electrodes suitable for use in commercial cells, reducing the electrode porosity was found to be a key parameter to obtain high-quality electrochemical performance. The triplite-type LiFeSO4F showed similar improvements upon PEDOT coating as the tavorite-type polymorph, but with lower capacity and less stable long-term cycling due to intrinsically sluggish kinetics and unfavorable particle morphology. Finally, the Li+-insertion/extraction process in tavorite LiFeSO4F was investigated. By thorough ex situ characterization of chemically and electrochemically prepared LixFeSO4F compositions (0≤x≤1), the formation of an intermediate phase, Li1/2FeSO4F, was identified for the first time. These findings helped redefine the (de)lithiation mechanism which occurs through two subsequent biphasic reactions, in contrast to a previously established single biphasic process.

Le développement de nouvelles fibres optiques en silice repose sur l’insertion des ions luminescents (ions de terres rares) dans des nanoparticules diélectriques. Dans ce contexte, la taille des particules est un paramètre clef qu’il convient de contrôler afin de bénéficier des nouvelles propriétés. Pour répondre à cet impératif, l’objectif de cette thèse était double. Premièrement, dans un objectif de structuration, il a été important d’étudier l’évolution des caractéristiques du matériau au cours de la fabrication, et deuxièmement, l’évolution des propriétés de luminescence avec les caractéristiques du matériau. La première partie de ce manuscrit décrit les différents types d’évolution des nanoparticules qui ont été observées au cours de ce travail de thèse. La réaction chimique de nanoparticules avec la matrice en silice est abordée dans l’étude du dopage par des nanoparticules de LaF3. Une observation originale de l’allongement et de la fragmentation de particules durant l’étirage en fibre optique est présentée. L’évolution thermodynamique des particules au cours de l’étirage, ainsi que l’influence des paramètres de l’étirage sont abordées. Enfin, la seconde partie de ce manuscrit se focalise sur le lien entre le matériau et ses propriétés spectroscopiques (Tm3+, Er3+). Les résultats montrent notamment que l’ajout de lanthane dans les fibres optiques dopées aux ions thulium augmente les pertes optiques, mais permet aussi d’augmenter la durée de vie du niveau 3H4 du Tm3+ jusqu’à un record de 58 μs pour une fibre transparente (pertes inférieures à 0,1 dB.m−1). Ces résultats confirment ainsi la nécessité d’un compromis sur la taille des particules et l’importance de ces travaux sur leurs possibilités de structuration. / The development of new silica-based optical fibers is relies on the insertion of luminescent ions (rare-earth ions) in dielectric nanoparticles. In this context, particle size is a key parameter that should be controlled in order to benefit from the new properties. To reach this goal, the objective of this thesis was twofold. Firstly, it was important to understand, to engineer its structuration, the evolution of the characteristics of the material during its fabrication process, and secondly, the evolution of the spectroscopic properties with the characteristics of the material. The first part of this manuscript describes the different types of evolution of the nanoparticles that were observed during this thesis work. The chemical reaction of nanoparticles with the silica matrix is discussed in the study of LaF3-nanoparticles doping. Also, an original observation of the elongation and the break-up of particles during the fiber drawing are presented. The thermodynamic evolution of the particles during the fabrication process as well as the influence of its parameters are discussed. Finally, the second part of this manuscript focuses on the link between the material and its spectroscopic properties (Tm3+, Er3+). In particular, the addition of lanthanum in the Tm3+-doped fibers increased the optical losses, but also enabled the increase of the lifetime of the 3H4 level up to a record in silica of 58 μs (optical losses below 0,1 dB.m−1). These results highlight the need for a compromise on particle size and the importance of this work on structuring possibilities.

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Nesta Dissertação de Mestrado foram estudadas as respostas inflamatórias e de reparo de tecido muscular de ratos a implantes de hidróxidos duplos lamelares (HDL) contendo íon cloreto e sulindaco (fármaco anti-inflamatório não-esteroidal - FAINE) em seu espaço interlamelar. As técnicas empregadas nesta investigação foram as espectroscopias Raman e de absorção no infravermelho (FTIR), a difratometria de raios X (XRD) e a análise histomorfológica dos tecidos corados pelas técnicas de Hematoxilina e Eosina (HE) (Michalany, 1990)(Michalany, 1990)(Michalany, 1990) e Picrosirius Red (Picro). Simulações do espectro vibracional foram feitas por DFT usando o pacote computacional Gaussian 09 e as análises estatísticas foram feitas usando o pacote Unscrambler X.10.1. Os experimentos in vivo foram realizados fazendo-se a implantação das pastilhas de HDL por microcirurgia entre as camadas do músculo externo oblíquo de ratos (Wistar) e como experimento controle foi feita a separação de tais camadas simulando um implante. Os tecidos foram coletados após 7, 21, 28 e 35 dias de pós operatório, divididos em duas porções (uma para análise histomorfológica e outra para análise por espectroscopia Raman). Inicialmente foram feitos os cálculos teóricos e a caracterização espectroscópica do sulindaco, que possibilitou melhorar sua atribuição vibracional encontrada na literatura. O mesmo ocorreu com as matrizes de HDL, de Zn(II) e de Mg(II), intercaladas com íons cloreto, o que também resultou em um aprimoramento da atribuição que é encontrada na literatura. Os dois HDLs intercalados com sulindaco também foram caracterizados espectroscopicamente e os espectros Raman mostraram grande semelhança com a espécie do fármaco desprotonado. O difratograma obtido dos intercalatos mostra expansão do espaçamento basal (de 7 Å para 26 Å) compatível com a intercalação do sulindaco inclinado em relação ao plano das lamelas. Os espectros Raman do tecido controle mostram alterações mais significativas nas banda amida I e amida III com o tempo de pós-operatório e por PCA foi possivel observar a nítida separação do grupo que apresenta um processo inflamatório agudo (7 dias). Os tecidos expostos à pastilha de HDL intercalada com íons cloreto, mostraram resposta inflamatória reduzida em relação ao tecido controle e as alterações espectrais observadas evidenciam a presença de colágenos, o que indica uma aceitação da pastilha por parte do organismo (biocompatibilidade). As pastilhas também foram analisadas espectroscopicamente e mostraram que houve incorporação de íons CO32- no espaço interlamelar, indicado pela presença da banda Raman em 1060 cm-1 (estiramento simétrico C-O nesse íon), mas não foi possivel determinar se eventuais variações no pH local exerceram efeitos na resposta inflamatória. No caso dos tecidos expostos à pastilha de HDL com sulindaco, a análise por microscopia Raman mostrou que o processo inflamatório foi significativamente reduzido, evidenciando uma ação local do fármaco, além do crescimento de colágenos do tipo III. A pastilha de HDL com sulindaco implantado foi analisada por FT-Raman e a liberação do fármaco foi confirmada. Os resultados de espectroscopia Raman de tecidos foram confirmados pela análise histomorfológica, que mostrou haver de fato um acúmulo de colágeno do tipo III nas regiões próximas às pastilhas implantadas, assim como a formação de invaginações e neovascularização. / In this Master\'s Thesis the inflammatory responses and tissue repair of rat muscles caused by implants of Lamellar Double Hydroxides (LDH) containing chloride ion and sulindac (anti-inflammatory non-steroidal drug - NSAID) in its interlayer space was studied. The techniques used in this research were the Raman spectroscopy and infrared absorption spectroscopy (FTIR), the X-ray diffraction (XRD) and the histomorphological analysis of tissues stained by techniques of Hematoxylin and Eosin (HE) and Picrosirius Red (Picro). Simulations of vibrational spectrum were made by DFT using the computational package Gaussian 09 and the statistical analyzes were performed using the Unscrambler X.10.1 package. In vivo experiments were performed by making the implantation of HDL tablets by microsurgery between the layers of the external oblique muscle of rats (Wistar) and as a control experiment the separation of the layers to simulate an implant was conducted. The tissues were collected after 7, 21, 28 and 35 days postoperatively, divided into two parts (one for histomorphological analysis and the other for analysis by Raman spectroscopy). Initially, theoretical calculations and spectroscopic characterization of sulindac where made, which enabled improving its vibrational assignment in the literature. The same happened for the LDH matrices, Zn(II) and Mg(II), both with chloride ions in the interlamelar space, which also resulted in an improving of it vibrational assignment found in the literature. Both LDH intercalated with sulindac were also characterized spectroscopically and their Raman spectra showed great agreement to the deprotonated species of thedrug. The diffraction pattern obtained from intercalated compounds shows an expansion of the basal spacing (7 Å to 26 Å) compatible with the hypothesis of the sulindac inclined relative to the lamelar plane. The Raman spectra control tissues show the most significant changes in the band amide I and amide III after diferente surgery times and through PCA was possible to observe the clear separation of the group that presenting an acute inflammatory process (at 7 days). Tissues exposed to LDH pellet intercalated with chloride ions showed a reduced inflammatory response relative to control tissue and the spectral changes demonstrate the presence of collagen, which indicates an acceptance of the insert by the body (biocompatibility). The pellets were also analyzed spectroscopically and showed that there was incorporation of CO32- ions in the interlayer space, indicated by the presence of the Raman band at 1060 cm-1 (symmetric stretch C-O of this ion), but it was not possible to determine if changes in local pH affect the inflammatory response. In the case of tissues exposed to LDH tablet with sulindac, analysis by Raman microscopy showed that inflammation was significantly reduced, indicating a local action of the drug, in addition, the collagen type III growth has been observed. The implanted LDH pellet with sulindac was analyzed by FT-Raman and the drug release was confirmed. The results of Raman spectroscopy of tissues were confirmed by histomorphological analysis, which showed that there is indeed an accumulation of collagen type III in the tissue regions near to the implanted pellets, as well as the formation of invagination and neovacularization.

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