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Les changements sociétaux tels que la personnalisation de la médecine, ainsi que la volonté de mieux comprendre la biologie de l’os modifie notre approche de fabrication des biomatériaux. Ces derniers se doivent ainsi d’être sur-mesure, c’est-à-dire capables de répondre à une problématique particulière. Ceci implique plus précisément dans le cas qui nous intéresse, à savoir l’os, la maîtrise de leur architecture et de leur comportement en milieu biologique (e.g., biodégradabilité).Malgré leurs atouts incontestables pour ce domaine, les biocéramiques en hydroxyapatite (HA) restent cantonnées à des usages modestes (e.g., comblement de petits défauts) ; en cause, des propriétés de biodégradation, d’ostéoconduction ou encore d’ostéoinduction souvent inadaptées aux problématiques contemporaines. Pour pallier ces limitations, nous avons entrepris deux voies de modulation des propriétés biologiques de l’HA, une voie « chimique », basée sur l’incorporation d’ions carbonate dans la structure apatitique, et une voie « procédé », reposant sur le potentiel de la fabrication additive.Des poudres d’hydroxyapatites phosphocalciques carbonatées (CHA) ont été préparées. Les ions carbonate pouvant occuper les sites hydroxyle et phosphate de l’HA, une méthode de quantification sélective du taux de substitution sur chacun de ces sites a été mise au point. Cette méthode spectroscopique novatrice ouvre de nombreuses opportunités d’études appliquées et fondamentales des CHA, abordées dans ce manuscrit, et constitue également un outil qui pourrait se révéler précieux dans l’optique de mise sur le marché de dispositifs médicaux en CHA (e.g., norme ISO).Basé sur une technologie de fabrication additive, un procédé de fabrication de biocéramiques d’architecture complexe, reproductible, flexible, fiable, de haute précision ( 5 µm) et peu coûteux, a été développé et optimisé. Cet outil de fabrication a été mis en œuvre pour répondre à des questions biologiques à finalité fondamentale et thérapeutique. / The current approach to produce biomaterials tends to evolve due to societal change such as the development of personalized medicine or the eagerness to better understand bone biology. Hence, biomaterials, which specifications depends of their intended applications, have to be custom made. For bone tissue engineering, this implies to control the scaffold architecture and behaviour in a biological environment (e.g., biodegradability).Despite their indisputable qualities, the use of hydroxyapatite (HA) bioceramics tend to be limited to basic applications (e.g. filling small defects) because of biodegradation, osteoconduction, or osteoinduction properties that do not match the actual needs. To exceed these limitations, we explored two modifications paths to tune HA biologic properties: a “chemical” approach based on incorporation of carbonate ions into apatitic structure, and a “process” approach, built around additive manufacturing singular potential.Carbonated phosphocalcic hydroxyapatites (CHA) powders were prepared. As carbonate ions may occupy HA hydroxyl and phosphate sites, a selective method to quantify their ratio in each site by IR spectroscopy has been developed. This innovative spectroscopic method opens numerous opportunities for applied and fundamental studies of CHA, but could also be considered as a precious standard for a future release of CHA medical devices (e.g. ISO norm).A cheap, flexible, robust and reliable manufacturing process based on an additive manufacturing technology has been developed and optimized, leading to the production of bioceramics with complex architectural features (accuracy  5 µm).This manufacturing process has been implemented in biological studies with fundamental and therapeutic purposes.

A insuficiência glótica é uma condição clínica caracterizada pelo fechamento inadequado das pregas vocais durante a fonação ou a deglutição. Nos casos mais leves, os pacientes são geralmente encaminhados para tratamento fonoterápico. Nos casos com sintomas mais importantes ou insucesso na fonoterapia, o tratamento cirúrgico se faz necessário. A melhor abordagem cirúrgica para a insuficiência glótica vem sendo debatida há mais de um século. As injeções laringoplásticas são procedimentos tecnicamente simples e com possibilidade de realização sob regime ambulatorial, no entanto seus resultados não são sempre previsíveis. Esses procedimentos também trazem consigo a possibilidade de rigidez da mucosa vocal por causa da reação inflamatória ao material utilizado. Apesar do crescente interesse por procedimentos ambulatoriais na laringologia e da popularização das injeções laringoplásticas, é sabido que se carece de materiais de melhor qualidade para resultados ainda mais consistentes. O surgimento do biopolímero de cana-de-açúcar (BPCA) e as pesquisas sobre seu uso em outras especialidades médicas apontaram para a possibilidade de que o referido material possa ser adequado ao uso nas injeções laringoplásticas. O presente trabalho foi desenvolvido para estudar a reação inflamatória causada pela injeção do BPCA na prega vocal de coelhos e comparar com a reação causada pela hidroxiapatita de cálcio (HCa). Para tal, foi procedida a injeção de 0,1mL HCa e BPCA na forma de gel nas pregas vocais direita e esquerda, respectivamente, de coelhos machos adultos da raça Oryctolagus cuniculus. Os coelhos foram divididos em dois grupos de 15, os quais foram sacrificados com 3 e 12 semanas. Após o sacrifício, foi feita a remoção e o processamento do material a ser estudado. Nos cortes histológicos foram avaliados os parâmetros de intensidade e composição celular do processo inflamatório, neovascularização, fibrogênese e alterações inflamatórias na mucosa vocal. Observou-se que a HCa e o BPCA desencadearam reação inflamatória por células do grupo linfomononuclear semelhantes em ambos os períodos analisados. A HCa desencadeou uma reação inflamatória por células gigantes intensa em todas as amostras e significativamente mais importante que o BPCA em ambos os períodos estudados. O BPCA apresentou reação inflamatória por células do grupo polimorfonucleares mais intensa do que a HCa apenas 3 semanas após a injeção. Não houve diferença entre as duas substâncias no que concerne à formação de tecido fibroso no leito cirúrgico após 3 e 12 semanas. Houve uma maior neoformação vascular com a injeção de BPCA comparado com a HCa após 3 semanas do procedimento. Não houve diferença estatística nessa variável após 12 semanas. Com relação às alterações inflamatórias da mucosa, não houve diferença significativa entre as substâncias nos três parâmetros estudados: integridade do epitélio, infiltrado inflamatório e presença de fibras colágenas na região submucosa. Conclui-se que, enquanto a HCa desencadeia uma reação inflamatória mediada por células gigantes, mais intensa e duradoura, o BPCA apresenta uma resposta por polimorfonucleares, assim como uma neoformação vascular mais importantes apenas após 3 semanas da injeção. Outros estudos devem ser realizados para avaliar o potencial do uso do BPCA no tratamento da insuficiência glótica / The glottal insufficiency is a clinical condition featured by abnormal closure of vocal folds during the process of phonation or deglutition. In most mild, cases patients are usually referred to speech therapy. In those cases presenting more relevant symptoms or failure in speech therapy, the surgical procedure is mandatory. The best surgical approach for glottal insufficiency has been debated over the past one hundred years. Laryngoplastic injections are technically simple procedures and possible to be performed in an outpatient basis, however their results are not always predictable. Such procedures may also present stiffness in the vocal mucosa due to the inflammatory reaction to the material which has been used. Despite of the fact that the growing interest in outpatient basis procedures in laryngology as well as the popularization of laryngoplastic injections, it is well known the lack of better quality materials for inducing much more consistent results. The arising of sugarcane biopolymer (SCB) along with researches on its use in other medical specialties demonstrated that there is a possibility for adequately using the mentioned material in laryngoplastic injections. The present work has been developed for the purpose of studying the inflammatory reaction which is caused by sugarcane biopolymer (SCB) injected in rabbits vocal folds as well as comparing to that reaction caused by calcium hydroxyapatite (HCa). For this experiment adult male rabbits from the race Oryctolagus cuniculus have been used, thus, 0.1 ml of HCa and of SCB in gel form were injected in their right and left vocal folds respectively. Rabbits have been divided into two groups of 15 each which were sacrificed at 3 and 12 weeks. After sacrifice, the vocal cords were removed and processed in order to be studied. Parameters as intensity and cellular composition in the inflammatory process, neovascularization, fibrogenesis as well as inflammatory alterations of vocal mucosa have been analyzed in histological pieces. It has been observed that HCa and SCB triggered an inflammatory reaction by lymphomononuclear group cells which are similar in the analysis of both periods. HCa triggered an inflammatory reaction by giant cells being intense in all of the samples and significantly more relevant as compared to SCB in the study of both periods. SCB presented an inflammatory reaction by polymorphonuclear group cells which was more intense as compared to HCa in just three weeks after injection. There was no difference between the two substances concerning the fibrous tissue building-up after three and twelve weeks. There was a larger vascular neoformation when injecting SCB as compared to HCa injection three weeks after procedure. There was no statistical difference in such a variable after twelve weeks. In respect of mucosa inflammatory changes, there was no significant difference between the substances by studying those three parameters as follows: epithelial integrity, inflammatory infiltrate and the presence of collagenous fibers in the submucosal region. In conclusion, while HCa triggers an inflammatory reaction mediated by giant cells which is more intense and lasting, SCB in its turn presents a more prevalent response by polymorphonuclear cells as well as by a vascular neoformation just three weeks after injection. Other studies should be done in order to evaluate the potential use of SCB in treating glottal insufficiency

Made available in DSpace on 2017-07-24T19:22:04Z (GMT). No. of bitstreams: 1 Fabio Goiris.pdf: 7029571 bytes, checksum: 63e1790a8a36324e4ac324716fcd8ddd (MD5) Previous issue date: 2017-02-15 / The objective of this study was to evaluate in vivo two new biomaterials for bone substitution – pure hydroxyapatite and collagen hydroxyapatite – aiming at determining their biocompatibility in soft tissues and their ability to enable bone neoformation in critical size defects in rats’ calvaria. Both types of synthetic hydroxyapatite were developed by the Chemistry department of the State University of Ponta Grossa – Pure hydroxyapatite (HaP) and Hydroxyapatite with collagen (HCol). The third synthetic hydroxyapatite used as a comparing element was the commercial hydroxyapatite Alobone® (HaAl), which is available in the Brazilian market. Experiment 1 was carried out with the animals’ dorsal connective tissue and used 45 Wistar female rats, divided randomly into three groups of 15 animals each (HaP, HaCol and HaAl) which were euthanized after 7, 15 and 30 days of operation.The histomorphometric exam after 30 days revealed the absence of inflammatory cell characteristic infiltrates and the presence of non-inflammatory collagen fibers. These results show the biocompatibility of the material implanted. Experiment 2 used 60 Wistar rats divided randomly into 4 groups (Group 1, HaP; Group 2, HaCol; Group 3, HaAl and Group 4, Control). Critical size defects of 8mm were performed in the calvaria and the three biomaterials were implanted. All groups also received collagen membrane. On day 30, inflammatory response on the defect was practically absent in all groups, mainly when compared to the period of 7 days. Some areas of bone neoformation were seen. There was predominance of osteoblasts, osteocytes and macrophages in lower amount. Regarding the radiographic aspect, after 30 days our study confirmed a marked biodegradation of the hydroxyapatite and signs of bone neoformation. The histomorphometric results of the synthetic hydroxyapatite implant demonstrated the probable occurrence of intramembranous ossification from the granulation tissue with the presence of bone-resident macrophages. It was possible to conclude that the results of our study in vivo can be used as a preliminary source of information about biocompatibility, biodegradability and bone neoformation from the implant of new biomaterials in vivo. / O objetivo desta pesquisa foi avaliar in vivo dois novos biomateriais de substituição óssea - hidroxiapatita pura e hidroxiapatita com colágeno - visando determinar a sua biocompatibilidade em tecidos moles e a sua capacidade de possibilitar a neoformação óssea em defeitos críticos em calvária de ratas. As duas formas de hidroxiapatitas sintéticas – Hidroxiapatita pura (HaP) e Hidroxiapatita com colágeno (HACol) - foram desenvolvidas pelo departamento de Química da Universidade Estadual de Ponta Grossa. A terceira hidroxiapatita sintética utilizada como elemento de comparação foi a hidroxiapatita comercial Alobone® (HaAl), disponível no mercado brasileiro. O experimento 1 realizado em conjuntivo de dorso de animais, utilizou 45 ratas fêmeas da espécie Wistar, divididos aleatoriamente em três grupos de 15 (HaP, HaCol e HaAl) e que sofreram eutanásia aos 7, 15 e 30 dias do pósoperatório. O exame histomorfométrico aos 30 dias verificou-se ausência do infiltrado característico de células inflamatórias e presença de fibras colágenas não inflamatórias. Estes resultados significam biocompatibilidade dos materiais implantados. O Experimento 2 utilizou 60 ratas Wistar divididos aleatoriamente em 4 grupos (Grupo 1, HaP; Grupo 2 HaCol, Grupo 3 HaAl) e Grupo 4, Controle). Realizaram-se defeitos críticos de 8 mm em calvária e a seguir colocaram-se os três tipos de biomateriais. Todos os grupos receberam também membrana de colágeno. Aos 30 dias, observou-se praticamente uma ausência da resposta inflamatória no local do defeito em todos os grupos, especialmente quando comparado ao período de 7 dias. Verificaram-se áreas de neoformação óssea. Houve predominância de osteoblastos, osteócitos e macrófagos em menor quantidade. No aspecto radiográfico, em 30 dias, a nossa pesquisa confirmou uma marcada biodegradação das hidroxiapatitas e sinais de neoformação óssea. Os resultados histomorfométricos da implantação de hidroxiapatitas sintéticas demonstraram a ocorrência de uma ossificação intramembranosa a partir do tecido de granulação com a participação de macrófagos ósseo-residentes. É possível concluir que os resultados dessa pesquisa podem ser utilizados como recurso preliminar de informações sobre biocompatibilidade, biodegradabilidade e neoformação óssea a partir da implantação de novos biomateriais in vivo.

A insuficiência glótica é uma condição clínica caracterizada pelo fechamento inadequado das pregas vocais durante a fonação ou a deglutição. Nos casos mais leves, os pacientes são geralmente encaminhados para tratamento fonoterápico. Nos casos com sintomas mais importantes ou insucesso na fonoterapia, o tratamento cirúrgico se faz necessário. A melhor abordagem cirúrgica para a insuficiência glótica vem sendo debatida há mais de um século. As injeções laringoplásticas são procedimentos tecnicamente simples e com possibilidade de realização sob regime ambulatorial, no entanto seus resultados não são sempre previsíveis. Esses procedimentos também trazem consigo a possibilidade de rigidez da mucosa vocal por causa da reação inflamatória ao material utilizado. Apesar do crescente interesse por procedimentos ambulatoriais na laringologia e da popularização das injeções laringoplásticas, é sabido que se carece de materiais de melhor qualidade para resultados ainda mais consistentes. O surgimento do biopolímero de cana-de-açúcar (BPCA) e as pesquisas sobre seu uso em outras especialidades médicas apontaram para a possibilidade de que o referido material possa ser adequado ao uso nas injeções laringoplásticas. O presente trabalho foi desenvolvido para estudar a reação inflamatória causada pela injeção do BPCA na prega vocal de coelhos e comparar com a reação causada pela hidroxiapatita de cálcio (HCa). Para tal, foi procedida a injeção de 0,1mL HCa e BPCA na forma de gel nas pregas vocais direita e esquerda, respectivamente, de coelhos machos adultos da raça Oryctolagus cuniculus. Os coelhos foram divididos em dois grupos de 15, os quais foram sacrificados com 3 e 12 semanas. Após o sacrifício, foi feita a remoção e o processamento do material a ser estudado. Nos cortes histológicos foram avaliados os parâmetros de intensidade e composição celular do processo inflamatório, neovascularização, fibrogênese e alterações inflamatórias na mucosa vocal. Observou-se que a HCa e o BPCA desencadearam reação inflamatória por células do grupo linfomononuclear semelhantes em ambos os períodos analisados. A HCa desencadeou uma reação inflamatória por células gigantes intensa em todas as amostras e significativamente mais importante que o BPCA em ambos os períodos estudados. O BPCA apresentou reação inflamatória por células do grupo polimorfonucleares mais intensa do que a HCa apenas 3 semanas após a injeção. Não houve diferença entre as duas substâncias no que concerne à formação de tecido fibroso no leito cirúrgico após 3 e 12 semanas. Houve uma maior neoformação vascular com a injeção de BPCA comparado com a HCa após 3 semanas do procedimento. Não houve diferença estatística nessa variável após 12 semanas. Com relação às alterações inflamatórias da mucosa, não houve diferença significativa entre as substâncias nos três parâmetros estudados: integridade do epitélio, infiltrado inflamatório e presença de fibras colágenas na região submucosa. Conclui-se que, enquanto a HCa desencadeia uma reação inflamatória mediada por células gigantes, mais intensa e duradoura, o BPCA apresenta uma resposta por polimorfonucleares, assim como uma neoformação vascular mais importantes apenas após 3 semanas da injeção. Outros estudos devem ser realizados para avaliar o potencial do uso do BPCA no tratamento da insuficiência glótica / The glottal insufficiency is a clinical condition featured by abnormal closure of vocal folds during the process of phonation or deglutition. In most mild, cases patients are usually referred to speech therapy. In those cases presenting more relevant symptoms or failure in speech therapy, the surgical procedure is mandatory. The best surgical approach for glottal insufficiency has been debated over the past one hundred years. Laryngoplastic injections are technically simple procedures and possible to be performed in an outpatient basis, however their results are not always predictable. Such procedures may also present stiffness in the vocal mucosa due to the inflammatory reaction to the material which has been used. Despite of the fact that the growing interest in outpatient basis procedures in laryngology as well as the popularization of laryngoplastic injections, it is well known the lack of better quality materials for inducing much more consistent results. The arising of sugarcane biopolymer (SCB) along with researches on its use in other medical specialties demonstrated that there is a possibility for adequately using the mentioned material in laryngoplastic injections. The present work has been developed for the purpose of studying the inflammatory reaction which is caused by sugarcane biopolymer (SCB) injected in rabbits vocal folds as well as comparing to that reaction caused by calcium hydroxyapatite (HCa). For this experiment adult male rabbits from the race Oryctolagus cuniculus have been used, thus, 0.1 ml of HCa and of SCB in gel form were injected in their right and left vocal folds respectively. Rabbits have been divided into two groups of 15 each which were sacrificed at 3 and 12 weeks. After sacrifice, the vocal cords were removed and processed in order to be studied. Parameters as intensity and cellular composition in the inflammatory process, neovascularization, fibrogenesis as well as inflammatory alterations of vocal mucosa have been analyzed in histological pieces. It has been observed that HCa and SCB triggered an inflammatory reaction by lymphomononuclear group cells which are similar in the analysis of both periods. HCa triggered an inflammatory reaction by giant cells being intense in all of the samples and significantly more relevant as compared to SCB in the study of both periods. SCB presented an inflammatory reaction by polymorphonuclear group cells which was more intense as compared to HCa in just three weeks after injection. There was no difference between the two substances concerning the fibrous tissue building-up after three and twelve weeks. There was a larger vascular neoformation when injecting SCB as compared to HCa injection three weeks after procedure. There was no statistical difference in such a variable after twelve weeks. In respect of mucosa inflammatory changes, there was no significant difference between the substances by studying those three parameters as follows: epithelial integrity, inflammatory infiltrate and the presence of collagenous fibers in the submucosal region. In conclusion, while HCa triggers an inflammatory reaction mediated by giant cells which is more intense and lasting, SCB in its turn presents a more prevalent response by polymorphonuclear cells as well as by a vascular neoformation just three weeks after injection. Other studies should be done in order to evaluate the potential use of SCB in treating glottal insufficiency

Orientadora: Daniele Botticelli / Banca: Idelmo Rangel Garcia Junior / Banca: Francisley Ávila Souza / Banca: Ronaldo Célio Mariano / Banca: Adolfo Embacher Filho / Resumo: Este trabalho teve por objetivo avaliar o tecido ósseo periimplantar formado após o enxerto sinusal com hidroxiapatita e beta-tricálcio fosfato (HA + -TCP), nas apresentações em grânulos e em pasta, concomitante à instalação de implantes em coelhos. Trinta e quatro seios maxilares de coelhos foram enxertados com HA + -TCP, sendo metade do grupo grânulos e metade do grupo pasta. Concomitantemente, foi realizada a instalação de implantes. Aos 7 e 40 dias pós-operatórios, realizou-se a eutanásia dos animais, e as amostras foram preparadas para as análises tomográfica, microtomográfica, histológica (coloração por hematoxilina e eosina - HE), imunoistoquímica (marcação de fator de transcrição Runt-2 - RUNX2 -, fator de crescimento endotelial vascular - VEGF -, osteocalcina - OCN - e fosfatase ácida resistente ao tartarato - TRAP) e de torque de remoção dos implantes. Na tomografia, foi observada a manutenção da integridade da membrana sinusal, sem extravasamento de material, nos dois grupos e períodos. Parâmetros morfométricos de volume ósseo, porcentagem do volume ósseo e número de trabéculas foram significativamente superiores para o grupo pasta do que para o grupo grânulos aos 7 dias, enquanto que a porosidade foi maior para o grupo grânulos nesse mesmo período. Aos 40 dias, não houve diferença significativa entre os grupos para a maioria dos parâmetros microtomográficos estudados. Nos cortes histológicos corados por HE, observou-se que em ambos os grupos ocorreu a formação d... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work aimed to evaluate the peri-implant bone tissue after maxillary sinus grafting with hydroxyapatite and beta-tricalcium phosphate (HA + -TCP), in granular and paste formulations, concomitant with implant placement in rabbits. Thirty four rabbit maxillary sinuses were grafted with HA + -TCP, being half of the granular group and half of the paste group. Concomitantly, the implant placement was performed. At 7 and 40 postoperative days, animals were euthanized, and the samples were prepared for tomographic, microtomographic, histological (hematoxylin and eosin staining), immunohistochemical (Runt-related transcription factor 2 - RUNX2, vascular endothelial growth factor - VEGF -, osteocalcin - OCN - and tartrate-resistant acid phosphatase - TRAP - staining) and implant torque removal analyses. In computed tomography, the maintenance of sinus membrane integrity, with no material extravasation, was observed in both groups and periods. Morphometric parameters of bone volume, percentage of bone volume and trabecular number were significantly higher for paste than granular group at day 7, while the porosity was higher for granular group in this period. At day 40, there were no significant differences between both groups for the majority of the microtomographic parameters studied. In the HE-stained histological sections, it was observed that bone healing around implant threads occurred for both groups at day 40, enhancing osseointegration. Similar positive immunostainings we... (Complete abstract click electronic access below) / Doutor

Les hydroxyapatites (HAps) sont des matériaux basiques qui présentent des propriétés catalytiques atypiques, notamment une sélectivité importante en butanol à partir de l’éthanol. Leur versatilité en termes de composition et de morphologie, facilement contrôlée par la synthèse, s’accompagne d’une grande modularité des propriétés acido-basiques de la surface, ce qui nous a permis d’établir des relations structure-réactivité dans l’objectif de rationaliser son mode de fonctionnement au niveau moléculaire. Certes, la stœchiométrie qui traduit le rapport Ca/P est un paramètre clé pour l’activité de ces matériaux dans ce type de réaction mais il s’avère que c’est plus précisément la concentration massique des OH des colonnes qui gouverne le niveau de la réactivité, ce qui oriente vers l’implication de ces espèces en tant que sites basiques. Au delà de cet aspect macroscopique, une approche visant la discrimination des contributions des OH-, PO43- et PO-H de surface et de cœur a été menée par IR et RMN du solide via des échanges isotopiques H-D, des prétraitements thermiques et des séquences RMN spécifiques. L’implication dans les interactions acides ou basiques des sites présents en surface a été suivie par adsorption de molécules sonde. L’adsorption du CO2 a révélé le caractère basique faible de la surface des HAps en générant des hydrogénocarbonates et des carbonates, respectivement suite à l’implication des OH basiques de terminaison en surface et des oxygènes de groupements phosphates. Seuls les OH qui émergent des colonnes sont impliqués dans l’interaction avec l’acétylène, conjointement avec les acides de BrØnsted PO-H (phosphates de terminaisons protonés). Les ions calcium sont peu accessibles (adsorption de CO et données XPS) et l’augmentation de leur accessibilité relative via la modulation de paramètres post-synthèse ne favorise pas la formation du n-butanol. Le suivi de la réaction de conversion d’éthanol en mode operando appuie la participation de la paire acide-base PO-H/OH dans le processus catalytique. L’étude de l’influence de la morphologie sur le comportement catalytique des HAps nous a incités à proposer qu’au-delà d’une réactivité favorisée sur les faces (001), l’allongement des particules bénéficie aussi au processus catalytique. Plus largement, le rôle joué par la mobilité des protons qui est un processus activé en température, permettrait d’unifier l’ensemble des données expérimentales qui rendent compte d’une sensibilité à la structure. / StructureHydroxyapatites (HAps) are basic materials which exhibit atypical catalytic properties, particularly a high selectivity in n-butanol from ethanol’s conversion. Versatility in terms of composition and morphology, easily tuned by synthesis, is accompanied by a high modularity of acid-base properties of the surface, which allowed us to establish structure-reactivity relationships in order to rationalize how the system works at a molecular level. Certainly stoichiometry, represented by the bulk Ca/P ratio, is a key parameter for the activity of these materials for this type of reaction, but it seems that the concentration of OH in the columns governs the conversion level, highlighting the role of these species as basic sites. Beyond this macroscopic aspect, an approach intended for the discrimination of the bulk and surface spectroscopic contributions of OH, PO43- and PO-H was implemented by IR and solid state NMR via H-D isotopic exchanges, thermal pretreatments and specific NMR sequences. The involvement of the present sites on the surface was investigated by adsorption of probe molecules. The CO2 adsorption revealed the low basicity of the surface generating hydrogenocarbonates and carbonates, respectively as a result of the interaction with the basic surface OH and oxygens of the phosphate groups. Only basic OH sites emerging from the columns are involved in the interaction with the acetylene, in association with Brönsted acids PO-H (protonated terminated phosphates). Calcium ions are inaccessible (CO adsorption and XPS data) and the increase of its relative accessibility via the modulation of the post-synthesis parameters does not promote the formation of n-butanol. Monitoring the reaction conversion of ethanol in operando mode supports the participation of the acid-base pair PO-H/OH in the catalytic process. The study of the influence of the morphology on the catalytic behavior of HAps led us to propose that beyond the enhancement of the reactivity on the (001) surfaces, the elongation of the particles is also beneficial to the catalytic process. The role of the protons mobility, activated by temperature, may unify all the experimental data that reflect a good sensitivity to the structure.

La substitution ionique apparait comme une des possibilités pour moduler la bioactivité de l’hydroxyapatite (HA), matériau couramment employé comme substitut osseux. L’incorporation simultanée d’ions carbonates et silicates dans la structure apatitique pourrait permettre de coupler les propriétés de résorption et de dissolution des apatites carbonatées avec le rôle métabolique important du silicium dans le tissu conjonctif.Des poudres d'hydroxyapatites phosphocalciques substituées en carbonates et en silicates de formule Ca10 x+y(PO4)6-x-y(CO3)x(SiO4)y(OH)2-x+y (avec 0 ≤ y ≤ x ≤ 2 et x+y ≤ 2, C Si HA), ont été synthétisées par précipitation en milieu aqueux. L’originalité de cette synthèse réside essentiellement dans l’emploi de réactifs parfaitement solubles et miscibles dans l’eau. L’incorporation des carbonates et des silicates en substitution des phosphates a lieu dès la précipitation. Les poudres obtenues sont monophasiques, cristallines et de structure apatitique.Les caractérisations physico-chimiques des poudres ont mis en évidence l’existence d’interactions entre les carbonates (A et B) et les silicates au sein de la maille apatitique. La décarbonatation des sites B, synonyme de décomposition de la phase C-Si-HA, a pu être décalée à de plus hautes températures avec l’emploi du CO2 comme atmosphère de calcination. Le frittage de céramiques denses et monophasiques en C Si HA destinée à une première évaluation biologique a donc été possible. La culture in vitro de cellules souches mésenchymateuses C3H10T1/2 à la surface de céramiques de composition C0,8 Si0,4 HA a mis en évidence leur biocompatibilité et des propriétés ostéoconductives équivalentes à celles de l’HA. / Ionic substitution appears as one possibility to modulate the bioactivity of hydroxyapatite (HA), which is a material commonly used as bone substitute due to its chemical and crystallographic similarities with bone mineral part. The simultaneous incorporation of silicates and carbonate ions in the apatite structure could allow coupling the resorption and dissolution properties of carbonate apatite with the important metabolic role of silicon in the connective tissue.Co-substituted hydroxyapatite powders, of assumed composition Ca10 x+y(PO4)6-x-y(CO3)x(SiO4)y(OH)2-x+y (with 0 ≤ y ≤ x ≤ 2 et x+y ≤ 2, C Si HA), with controlled amount of carbonate (x) and silicate groups (y), were synthesized by means of a wet precipitation method. The innovative character of this synthesis process lies in the use of completely soluble and miscible reagents in water. According to this method, silicates and carbonates substitution for phosphate ions into the apatitic structure occurs from precipitation. The powders obtained are monophasic, crystalline and apatitic.The physicochemical characterizations of powders revealed the existence of interactions between carbonates (A and B) and silicates within the apatitic structure. C Si HA phase decomposes when B-type carbonate are released from the structure. The use of CO2 throughout the heat treatment allows to shift the B sites decarbonatation to higher temperature than under inert atmosphere. The sintering of dense and monophasic ceramic in C Si HA was realized. In vitro culture of mesenchymal stem cells C3H10T1/2 on the surface ceramics showed equivalent biocompatibility and osteoconductive properties between HA and C-Si-HA (x=0.8, y=0.4) phases.

Este trabalho, conduzido na forma de 2 subprojetos, avaliou: 1) o potencial preventivo de pastas à base de hidroxiapatita (nanopartículas de fosfato de cálcio) sobre a erosão e a abrasão do esmalte e dentina bovinos in vitro e in situ e 2) o efeito de um bochecho com solução de lactato de cálcio antes da escovação com dentifrício fluoretado sobre a erosão associada ou não à abrasão do esmalte e dentina bovinos in vitro e in situ. Na fase in vitro do 1o subprojeto, submeteram-se blocos de esmalte e dentina bovinos, por 5 dias, à erosão (coca-cola, pH 2,6, 4x/dia, 90s cada) + abrasão (escova elétrica + solução do dentifrício sem flúor, 10s cada, 2x/dia) e os tratamentos foram realizados após a abrasão, através da aplicação das seguintes pastas sobre os blocos (3 min, 2x/dia): 10% HAP, 10% HAP + 0,2% NaF, 20% HAP, 20% HAP + 0,2% NaF, 20% HAP + 2% NaF, placebo, 0,2% NaF, 2% NaF, MI paste, MI paste plus e controle. Na fase in situ, (4 fases, 5 dias/cada), 12 voluntários utilizaram dispositivo intrabucal palatino contendo 4 blocos de dentina e 4 de esmalte bovinos divididos nas condições: erosão e erosão+abrasão. Em cada fase foi feito tratamento com uma das seguintes pastas: 10% HAP, 10% HAP + 0,2% NaF, MI paste plus ou Placebo. O protocolo erosivo e abrasivo foi semelhante ao in vitro. No 2o subprojeto, a fase in vitro foi semelhante ao subprojeto 1, porém apresentou as condições erosão e erosão+abrasão. O estudo compreendeu os seguintes tratamentos: BCa + DF, BCa + DP, BP + DF e BP + DP. Após erosão, os blocos foram imersos em água deionizada (BP) ou solução de lactato de cálcio 150 mM (BCa; 1 min, sob agitação). Na condição erosão apenas, a solução de dentifrício fluoretado (DF) ou placebo (DP) foi pipetada sobre as amostras. A fase in situ foi semelhante ao experimento in vitro, porém com 15 voluntários e escovação por 15 s. A variável de resposta para os 2 subprojetos foi a análise de desgaste, avaliada por perfilometria (&#x3BC;m) e para a fase in situ do 1o subprojeto foi realizada também a análise por MEV-EDS. Os dados foram analisados pelos testes ANOVA/Tukey, Kruskal-Wallis/Dunn ou ANOVA a dois critérios/Bonferroni (p<0,05). In vitro, para o esmalte, as pastas à base de hidroxiapatita (10 e 20%), independentemente da presença do F, foram efetivas na prevenção da erosão associada à abrasão. Para a dentina, o efeito protetor foi encontrado apenas para as pastas contendo F, maior para aquelas com concentração mais elevada. In situ, apenas a pasta contendo 10% HAP foi efetiva para reduzir a erosão em esmalte quando comparada à pasta placebo. Nas demais condições testadas nenhuma das pastas utilizadas diferiu significativamente da placebo. Para o segundo subprojeto, o BCa + DF teve um efeito protetor apenas para a erosão de esmalte e dentina in vitro. Para a erosão associada à abrasão in vitro, assim como no estudo in situ, não houve diferença significativa entre os tratamentos. / This study, conducted in the form of two subprojects, evaluated: 1) the preventive potential of hydroxyapatite-based (calcium phosphate nanoparticles) pastes on erosion and abrasion of bovine enamel and dentin in vitro e in situ and 2) the effect of rinsing with a solution of calcium lactate before brushing with fluoride toothpaste on erosion associated or not with abrasion of bovine enamel and dentin in vitro e in situ. In the in vitro phase of the 1st subproject, bovine enamel and dentin blocks were submitted to erosion (coca-cola, pH 2.6, 4x/day, 90s each) + abrasion (electric toothbrush + fluoride-free toothpaste slurry, 10s each, 2x/day) for 5 days. Treatments were performed after abrasion, by applying the following pastes on the blocks (3 min, 2x/day): 10% HAP, 10% HAP + 0.2% NaF, 20% HAP, 20% HAP + 0.2% NaF, 20% HAP + 2% NaF, placebo, 0.2% NaF, 2% NaF, MI paste, MI paste plus and control. In the in situ phase (4 phases, 5 days each), 12 volunteers used intraoral palatal appliance containing four blocks of dentin and four blocks enamel divided into conditions erosion and erosion+abrasion. In each phase, treatment was done with one of the following pastes: 10% HAP, 10% HAP + 0.2% NaF, MI paste plus or Placebo. The erosive and abrasive protocol was similar to the in vitro phase. In the 2nd subproject, the in vitro phase was similar to subproject 1, but presented both conditions erosion and erosion + abrasion. The study included the following treatments: BCa + DF, BCa + DP, BP + DF e BP + DP. After erosion, the blocks were immersed in deionized water (BP) or calcium lactate solution 150 mM (BCa; 1 min, stirring). For the condition erosion only, the slurry of fluoride (DF) or placebo (DP) dentifrice was pipetted on the samples. The in situ phase was similar to the in vitro experiment, but 15 volunteers were included and brushing was conducted for 15 s. The response variable for the two subprojects was wear, evaluated by profilometry (&#x3BC;m). For the in situ phase of the 1st subproject, SEM-EDS was also performed. Data were analyzed by ANOVA/Tukey, Kruskal-Wallis/Dunn or two-way ANOVA/Bonferroni tests (p <0.05). In vitro , for enamel, 10 and 20% hydroxyapatitebased pastes, regardless the presence of F, were effective in preventing erosion associated with abrasion. For dentin, the protective effect was found only for Fcontaining paste and the effect was higher for those with higher F concentration. In situ, only pastes containing 10% HAP were effective in reducing enamel erosion as compared to the placebo paste. For the other tested conditions, none of the pastes used significantly differed from placebo. For the second subproject, the BCa + DF had a protective effect only for enamel and dentin erosion in vitro . For erosion associated with abrasion in vitro , as well as for the in situ study, no significant differences were detected among the treatments.

La substitution ionique apparait comme une des possibilités pour moduler la bioactivité de l'hydroxyapatite (HA), matériau couramment employé comme substitut osseux. L'incorporation simultanée d'ions carbonates et silicates dans la structure apatitique pourrait permettre de coupler les propriétés de résorption et de dissolution des apatites carbonatées avec le rôle métabolique important du silicium dans le tissu conjonctif.Des poudres d'hydroxyapatites phosphocalciques substituées en carbonates et en silicates de formule Ca10 x+y(PO4)6-x-y(CO3)x(SiO4)y(OH)2-x+y (avec 0 ≤ y ≤ x ≤ 2 et x+y ≤ 2, C Si HA), ont été synthétisées par précipitation en milieu aqueux. L'originalité de cette synthèse réside essentiellement dans l'emploi de réactifs parfaitement solubles et miscibles dans l'eau. L'incorporation des carbonates et des silicates en substitution des phosphates a lieu dès la précipitation. Les poudres obtenues sont monophasiques, cristallines et de structure apatitique.Les caractérisations physico-chimiques des poudres ont mis en évidence l'existence d'interactions entre les carbonates (A et B) et les silicates au sein de la maille apatitique. La décarbonatation des sites B, synonyme de décomposition de la phase C-Si-HA, a pu être décalée à de plus hautes températures avec l'emploi du CO2 comme atmosphère de calcination. Le frittage de céramiques denses et monophasiques en C Si HA destinée à une première évaluation biologique a donc été possible. La culture in vitro de cellules souches mésenchymateuses C3H10T1/2 à la surface de céramiques de composition C0,8 Si0,4 HA a mis en évidence leur biocompatibilité et des propriétés ostéoconductives équivalentes à celles de l'HA.