Novos tipos de sílicas mesoporosas esféricas (SMEs) com tamanho de partícula entre 3 e 10 µm foram sintetizadas utilizando os copolímeros tribloco EO17PO60EO17 (P103) ou EO26PO39EO26 (P85) como direcionadores de estrutura. As SMEs foram preparadas via um processo de síntese com duas etapas de tratamento hidrotérmico (TH) em forno convencional, utilizando o ortosilicato de tetraetila como fonte de sílica, os surfatantes P103 ou P85 como moldes em combinação com o co-surfatante brometo de cetiltrimetilamônio (CTAB) e o co-solvente etanol, sob condições ácidas. As SMEs obtidas foram caracterizadas por microscopia eletrônica de varredura (MEV) e medidas de adsorção/dessorção de N2. O volume e o tamanho do poro das SMEs podem ser aumentados com o aumento da temperatura do TH. O volume e o tamanho do poro (0,41 cm3g-1; 2,84 nm) da amostra sintetizada com P103 aumentaram (1,20 cm3g-1; 4,32 nm) quando a temperatura do TH aumentou de 80°C para 120°C na segunda etapa do TH. O aumento do volume e do tamanho de poro também pode ser obtido utilizando um único tratamento hidrotérmico, porém empregando 1,3,5-trimetilbenzeno (TMB) como agente dilatador de poros. O volume e o tamanho do poro (0,34 cm3g-1; 2,02 nm) da amostra sintetizada com P85 sem TMB aumentaram (0,37 cm3g-1; 2,51 nm) na amostra preparada com P85 e TMB. As características texturais e de superfície dos materiais obtidos com P103 e P85 foram comparadas com um material sintetizado em paralelo, nas mesmas condições experimentais, utilizando o copolímero EO20PO70EO20 (P123) como direcionador de estrutura e CTAB como co-surfatante. A SME sintetizada com P103 foi usada como adsorvente de compostos orgânicos voláteis (COVs) oriundos de misturas padrões. Os componentes da mistura padrão foram então removidos do adsorvente (sílica) por dessorção térmica e introduzidos em uma coluna cromatográfica para separação por cromatografia a gás (CG) e identificação por espectrometria de massa (EM). Esta SME foi também testada como adsorvente de uma amostra de ar coletada em uma rua com significativo fluxo de veículos. O ar foi coletado paralelamente na SME e num adsorvente comercial (Tenax TA/Carbotrap). Os compostos n-hexano, benzeno, tolueno e o-xileno, oriundos de emissões veiculares, foram encontrados em ambos adsorventes (sílica e Tenax TA/Carbotrap). O fármaco Rifampicina foi encapsulado numa SME sintetizada com P123/CTAB e na sílica SBA-15 (poros ordenados hexagonalmente). A encapsulação do fármaco (cerca de 30%) em ambas as sílicas foi confirmada pelos resultados de adsorção/dessorção de N2. / New types of mesoporous silica spheres with particle diameter of 3 - 10 µm were synthesized by using a triblock copolymer EO17PO60EO17 (P103) or EO26PO39EO26 (P85) as templates. The microspheres were prepared via a two-step hydrothermal treatment (HT) in an oven by using tetraethoxysilane as silica source, the surfactants P103 or P85 as templates in combination with a cosurfactant cetyltrimethylammonium bromide (CTAB) and a cosolvent ethanol, under acidic conditions. The obtained silica spheres in both procedures were characterized by scanning electron microscopy (SEM) and N2 sorption technique. The volume and the pore size of the silica spheres can become greater by increasing the temperature of the HT. The volume and the pore size (0.41 cm3g-1; 2.84 nm) of the sample prepared with P103 became greater (1.20 cm3g-1; 4.32 nm) when the temperature of HT increased by 80°C to 120°C in the second step of the HT. The volume and the pore size can also be increased using 1,3,5-trimethylbenzene (TMB) as a swelling agent, instead of raising the temperature of the HT. The volume and the pore size (0.34 cm3g-1; 2.02 nm) of the sample prepared with P85 without TMB became greater (0.37 cm3g-1; 2.51 nm) in the sample prepared with P85 and TMB. The characteristics of textures and surfaces of the materials synthesized by using P103 or P85 were compared with a material prepared with the copolymer EO20PO70EO20 (P123) as template using the same experimental conditions. The silica microspheres synthesized with P103 were used as adsorbents for volatile organic compounds (VOCs) from standard mixtures. The compounds of the standard mixture were then removed from the adsorbent (silica) by thermal desorption and introduced into a chromatographic column for separation by gas chromatography (GC) and identification by mass spectrometry (MS). This material was also used as adsorbent of an air sample collected on a street with a significant flow of motor vehicles. The air was collected on the silica and on a commercial adsorbent (Tenax TA/Carbotrap) one by one. The compounds n-hexane, benzene, toluene and o-xylene, resulted from the emissions from vehicles, were found in both adsorbents (silica and Tenax TA/Carbotrap). The drug Rifampicin was encapsulated in the mesoporous spherical silica, prepared with P123/CTAB and in the silica SBA-15 (hexagonally ordered pores). The encapsulation of the drug (about 30%) in both the silica was confirmed by measurements of adsorption/desorption of N2

Novos tipos de sílicas mesoporosas esféricas (SMEs) com tamanho de partícula entre 3 e 10 µm foram sintetizadas utilizando os copolímeros tribloco EO17PO60EO17 (P103) ou EO26PO39EO26 (P85) como direcionadores de estrutura. As SMEs foram preparadas via um processo de síntese com duas etapas de tratamento hidrotérmico (TH) em forno convencional, utilizando o ortosilicato de tetraetila como fonte de sílica, os surfatantes P103 ou P85 como moldes em combinação com o co-surfatante brometo de cetiltrimetilamônio (CTAB) e o co-solvente etanol, sob condições ácidas. As SMEs obtidas foram caracterizadas por microscopia eletrônica de varredura (MEV) e medidas de adsorção/dessorção de N2. O volume e o tamanho do poro das SMEs podem ser aumentados com o aumento da temperatura do TH. O volume e o tamanho do poro (0,41 cm3g-1; 2,84 nm) da amostra sintetizada com P103 aumentaram (1,20 cm3g-1; 4,32 nm) quando a temperatura do TH aumentou de 80°C para 120°C na segunda etapa do TH. O aumento do volume e do tamanho de poro também pode ser obtido utilizando um único tratamento hidrotérmico, porém empregando 1,3,5-trimetilbenzeno (TMB) como agente dilatador de poros. O volume e o tamanho do poro (0,34 cm3g-1; 2,02 nm) da amostra sintetizada com P85 sem TMB aumentaram (0,37 cm3g-1; 2,51 nm) na amostra preparada com P85 e TMB. As características texturais e de superfície dos materiais obtidos com P103 e P85 foram comparadas com um material sintetizado em paralelo, nas mesmas condições experimentais, utilizando o copolímero EO20PO70EO20 (P123) como direcionador de estrutura e CTAB como co-surfatante. A SME sintetizada com P103 foi usada como adsorvente de compostos orgânicos voláteis (COVs) oriundos de misturas padrões. Os componentes da mistura padrão foram então removidos do adsorvente (sílica) por dessorção térmica e introduzidos em uma coluna cromatográfica para separação por cromatografia a gás (CG) e identificação por espectrometria de massa (EM). Esta SME foi também testada como adsorvente de uma amostra de ar coletada em uma rua com significativo fluxo de veículos. O ar foi coletado paralelamente na SME e num adsorvente comercial (Tenax TA/Carbotrap). Os compostos n-hexano, benzeno, tolueno e o-xileno, oriundos de emissões veiculares, foram encontrados em ambos adsorventes (sílica e Tenax TA/Carbotrap). O fármaco Rifampicina foi encapsulado numa SME sintetizada com P123/CTAB e na sílica SBA-15 (poros ordenados hexagonalmente). A encapsulação do fármaco (cerca de 30%) em ambas as sílicas foi confirmada pelos resultados de adsorção/dessorção de N2. / New types of mesoporous silica spheres with particle diameter of 3 - 10 µm were synthesized by using a triblock copolymer EO17PO60EO17 (P103) or EO26PO39EO26 (P85) as templates. The microspheres were prepared via a two-step hydrothermal treatment (HT) in an oven by using tetraethoxysilane as silica source, the surfactants P103 or P85 as templates in combination with a cosurfactant cetyltrimethylammonium bromide (CTAB) and a cosolvent ethanol, under acidic conditions. The obtained silica spheres in both procedures were characterized by scanning electron microscopy (SEM) and N2 sorption technique. The volume and the pore size of the silica spheres can become greater by increasing the temperature of the HT. The volume and the pore size (0.41 cm3g-1; 2.84 nm) of the sample prepared with P103 became greater (1.20 cm3g-1; 4.32 nm) when the temperature of HT increased by 80°C to 120°C in the second step of the HT. The volume and the pore size can also be increased using 1,3,5-trimethylbenzene (TMB) as a swelling agent, instead of raising the temperature of the HT. The volume and the pore size (0.34 cm3g-1; 2.02 nm) of the sample prepared with P85 without TMB became greater (0.37 cm3g-1; 2.51 nm) in the sample prepared with P85 and TMB. The characteristics of textures and surfaces of the materials synthesized by using P103 or P85 were compared with a material prepared with the copolymer EO20PO70EO20 (P123) as template using the same experimental conditions. The silica microspheres synthesized with P103 were used as adsorbents for volatile organic compounds (VOCs) from standard mixtures. The compounds of the standard mixture were then removed from the adsorbent (silica) by thermal desorption and introduced into a chromatographic column for separation by gas chromatography (GC) and identification by mass spectrometry (MS). This material was also used as adsorbent of an air sample collected on a street with a significant flow of motor vehicles. The air was collected on the silica and on a commercial adsorbent (Tenax TA/Carbotrap) one by one. The compounds n-hexane, benzene, toluene and o-xylene, resulted from the emissions from vehicles, were found in both adsorbents (silica and Tenax TA/Carbotrap). The drug Rifampicin was encapsulated in the mesoporous spherical silica, prepared with P123/CTAB and in the silica SBA-15 (hexagonally ordered pores). The encapsulation of the drug (about 30%) in both the silica was confirmed by measurements of adsorption/desorption of N2

Victor H. Yngve. / Cover title. "Reprint from Proceedings of the American Philosophical Society, vol.104, no.5." / Includes bibliographical references.

According to the Encoding Model, speakers communicate by encoding the propositions they want to communicate into sentences, in accordance with the conventions of a language L. By uttering a sentence that encodes p, the speaker says that p. Communication is successful only if the audience identifies the proposition that the speaker intends to communicate, which is achieved by decoding the uttered sentence in accordance with the conventions of L. A consequence of the Encoding Model has been the proliferation of underdetermination arguments, each of which concludes against some linguistic theory T, on the grounds that, were T true, audiences would be unable to know what was said by utterances of some particular linguistic form, and therefore unable to know what speakers intended to communicate by these utterance. The result, if we accept the conclusion of these arguments, is radical restriction of the domain of viable linguistic theory. This Thesis defends an alternative model according to which there need be nothing encoded in an uttered sentence – nothing that is said by its utterance – for the audience to retrieve. Rather, there are indefinitely many ways to interpret uttered sentences – indefinitely many routes to the propositions that speaker intend to communicate – which proceed through different interpretations of what is said.

Dans ce travail, nous avons élaboré, par voie sol-gel, un nouveau verre bioactif mésoporeux : 92S6 (92% SiO2, 6% CaO, et 2% P2O5). Cette synthèse a été développée en variant les paramètres telles que la température, la nature du tensioactif (ionique (le CTAB) ou non ionique (le P123)) et la longueur de la chaîne carbonée pour chaque type de tensioactif et en étudiant leurs effets sur les propriétés texturales du verre. Des études physico-chimiques et biologiques in vitro ont été menées sur ces biomatériaux. Par la suite, nous avons réalisé une étude structurale de l'eau confinée dans les pores du verre synthétisé qui a révélé une modification de l'ordre locale en comparaison avec l'état massique (bulk). Ceci permet un contrôle de la quantité de principe actif à incorporer dans les pores, du taux d'adsorption et de la cinétique de libération. La diffraction des Rayons X aux petits angles, l'analyse texturale par BET et les images de la microscopie électronique en transmission ont mis en évidence l'influence des paramètres de synthèse sur les propriétés texturales des verres synthétisés. En effet, l'échantillon synthétisé avec le tensioactif ionique (CTAB) présente une structure mésoporeuse non ordonné, alors que l'utilisation du tensioactif non-ionique (P123) favorise l'obtention d'un verre mésoporeux ayant une structure poreuse ordonnée. Dans le cas des verres synthétisés avec les différentes longueurs de la chaîne carbonée des tensioactifs, nous avons démontré que la longueur de la chaîne alkyle du tensioactif ionique détermine la morphologie des particules et les caractéristiques texturales des 3 verres, alors que nous avons noté une absence de différences significatives dans la texture des matériaux dans le cas des 3 verres synthétisés avec les tensioactifs non ioniques. Nous avons aussi mis en évidence l'influence de la température de synthèse sur les propriétés texturales des verres synthétisés. Nous avons démontré que la température de synthèse agit sur le diamètre des pores de manière différente selon la nature du tensioactif. L'augmentation de la température de synthèse conduit à une augmentation de la dimension des cavités dans le cas des verres synthétisés avec le P123, alors que dans le cas des verres synthétisés avec le tensioactif ionique CTAB, l'augmentation de la température de synthèse conduit à une diminution des diamètres des pores. Nous avons démontré que la morphologie des particules et les caractéristiques texturales des verres influent sur la bioactivité de ces derniers. Nous avons obtenu des verres bioactifs comme en témoigne la formation de la couche d'hydroxyapatite à leurs surfaces une fois immergés dans le SBF, ce qui explique l'intérêt des ces verres dans le domaine de la chirurgie orthopédique. / In this study, a new mesoporous bioactive glass 92S6 (92% SiO2, 6% CaO, and 2% P2O5), was prepared by sol-gel method. The purpose of this study was first to investigate the effect of synthesis parameters such as aging temperature, surfactant type and surfactant carbon chain length on the glass textural properties and then to investigate these effect on the glass bioactivity. Then, we conducted a structural study of water confined in the pores of the synthesized glass. This study revealed a change of the local order of confined water in comparison with the bulk. This allows control of drugs to be incorporated into the pores, the adsorption rate and the release kinetics. The small-angle XRD patterns (SAXRD), the Brunauer–Emmett–Teller (BET) method and the Transmission Electron Microscopy (TEM) studies evidence the influence of the structure-directing agent (ionic surfactant CTAB or non-ionic P123) in the generation of unorganized or well ordered pores in the 92S6 glass. We also demonstrated that when we synthesized glasses with a same composition using the same technique (sol-gel), in presence of surfactants with different carbon chain length, there is a direct correlation between the surfactant and textural properties and structural characteristics. As observed from small-angle XRD patterns and TEM images, synthesis at different temperatures lead to the formation of mesoporous glasses. The properties of these glasses are extremely dependent on the synthesis temperature. We demonstrated also that the bioactivity may be significantly modified by a change on glass textural properties. Finally, the samples were analyzed to quantify the apatite formation ability when soaked in SBF solution. The physico-chemical studies showed apatite-like phases formed at the glasses surface when soaked in SBF. So, our mesoporous glasses are bioactive. These characteristic mesoporous glasses will display good future applications in bone tissue repairing and engineering.