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The reaction of hydroquinone and 1,12-dibromododecane affords 4-(12-bromo-dodecyloxy)phenol (4, 7% yield). The alkyl bromide (4) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyloxy)phenol (1) in 52% yield. The reaction of t-butyllithium with 4-bromoanisole followed by reaction with 1-12-dibromododecane affords a mixture of 4-bromoanisole, 1,12-dibromododecane ,and 4-(12-bromododecyl)-anisole (6). Silica gel chromatography resulted in an inseperable mixture of 4-bromoanisole and (6). Reaction of the mixture with BBr3 afforded 4-(12-bromododecyl)phenol (7) in 34% yield. The alkyl bromide (7) was converted to the corresponding thiol with thiourea to afford 4-(12-mercaptododecyl)phenol (2) in 9% yield. Reduction of 16-mercaptohexadecanoic acid with BH3â hTHF afforded 16-mercaptohexadecanol (3) in 53% yield. All new compounds were characterized by ¹H NMR, ¹³C NMR, transmission IR, HRMS, and, where possible, elemental microanalysis. Self-assembled monolayers (SAMs) on gold were prepared using thiols 1, 2, and 3. SAMs were characterized using reflectance-absorbance infrared spectroscopy (RAIRS). Diagnostic vibrational modes were assigned by comparing RAIRS spectra to normal mode frequencies and intensities calculated using DFT methods at the 6-31G* level using commercial software. Water droplet goiniometry found contact angles of 52o, 53o, and 64o for SAMs prepared from 1, 2, and 3, respectively. SAMs of 1 and 2 were found to be hydrophilic. When SAMs prepared from 1, 2, and 3 were silylated with phenyldimethylchlorosilane, the resulting contact angles were 78o, 74o, and 75o respectively. A significant increase in contact angles for silylated SAMs of 1 and 2 indicated facile silanization of the surface hydroxides. RAIRS spectra were also obtained for the functionalized SAMs. Silylated SAMs prepared from 1, 2, and 3 are currently under investigation as models for silica-immobilized metallocene olefin polymerization catalysts. / Master of Science

Isotermas de adsorção de anfifílicos sintéticos formadores de bicamadas ou fosfolipídios a partir de vesículas sobre partículas de sílica hidrofílica (AEROSIL OX-50) foram obtidas em diversas condições experimentais. Vesículas pequenas de fosfatidilcolina (PC), dipahnitoilfosfatidilcolina (DPPC), dihexadecilfosfato (DHP) e brometo de dioctadecildimetilamônio (DODAB) dispersas em 10 mM de dois diferentes tampões (Tris ou HEPES) em 3 diferentes valores de pH apresentam afinidades pela sílica que seguem a seqüência: DODAB>DPPC>PC>DHP. Deposição de bicamada de fosfolipídio é favorecida pela presença de Tris como tampão em pH ≤ 7,4, e temperaturas acima da temperatura de transição de fase para bicamada de fosfolipídio. Interação a 65 ºC por 1 hora entre vesículas de DPPC e sílica eficientemente gera a deposição de bicamada com uma adsorção máxima, se Tris é o tampão utilizado. Consistentemente, a molhabilidade de superfícies planares de SiO2 em condições de deposição de bicamada (como descrita pelas isotermas de adsorção) na presença de vesículas lipídicas mostra um grande aumento da hidrofobicidade da superfície para vesículas de DPPC a 65 ºC e DODAB em temperatura ambiente. Redução na absorção de luz pela MC540 em 565 nm foi usada como indicativa de deposição de bicamada sobre partículas de sílica. Durante a interação com partículas sólidas, a absorbância a 565 nm mostra uma diminuição que corresponde a porcentagem de marcador que se intercala entre a bicamada e a partícula sólida e, conseqüentemente, se esconde da luz incidente. Para DPPC, à 65 ºC, e DODAB à temperatura ambiente, mas não para PC, a ocorrência de deposição de bicamada, descrita pelas isotermas de adsorção, é confirmada pelas três técnicas empregadas para detecção. / Adsorption isotherms of bilayer-forming synthetic amphiphiles or phospholipids from vesicles onto hydrophilic silica particles (AEROSIL 0X-50) are obtained over a range of experimental conditions. Phosphatidylcholine (PC), dipalmitoylphosphatidylcholine (DPPC), and dioctadecyldimethylammonium bromide (DODAB) dispersed in 10 mM of two different buffers (Tris or HEPES) at 3 different pH values as small unilamellar vesicles present affinities for silica following the sequence: DODAB > DPPC > PC. Deposition of phospholipid bilayers was favoured by the presence of Tris as buffer, pH≤ 7.4, and temperatures above the phase transition temperature (Tc) for the phospholipid bilayer. Interaction at 65 ºC for 1 h between DPPC vesicles and silica efficiently leads to bilayer deposition at maximal adsorption, if Tris is the buffer used. Consistently, wettability of SiO2 planar surfaces precisely under conditions of bilayer deposition (as depicted from the isotherms) in the presence of the lipidic vesicles yielded a large increase on surface hydrophobicity for DPPC at 65 ºC and DODAB at room temperature. Reduction of merocyanine 540 absorbance at 565 nm was used as a marker for bilayer deposition onto the silica particles. Upon interaction with the solid particle, absorbance at 565 nm displays a decrease with rime that corresponds to the percentage of dye that became sandwiched between the bilayer and the solid particle surface and thereby hidden from the incident light. For DPPC at 65 ºC and DODAB at room temperature, but not for PC, occurrence of bilayer deposition depicted from the adsorption isotherms is confirmed from the three techniques employed for detection.

Resumo: A sílica mesoporosa do tipo MSU-4 foi sintetizada a partir do agente direcionador de estrutura Tween 20, utilizado como molde, e do precursor inorgânico tetraetilortosilicato (TEOS). Estruturas mesoporosas tem sido aplicadas em estudos luminescentes por apresentarem alto índice de organização, grande área superficial e distribuição regular de tamanho de poros. Nesse trabalho a sílica mesoporosa foi funcionalizada com 3-aminopropiltrietoxisilano (APTES) para aplicação luminescente. A sílica mesoporosa funcionalizada foi caracterizada por difração de raios-X a baixo ângulo (SAXS), espectroscopia no infravermelho (FT-IR) e adsorção e dessorção de nitrogênio (BET). O material luminescente foi preparado pela formação do complexo [Eu(tta)3] em meio metanólico e impregnado nos canais da sílica mesoporosa. Para a impregnação, o íon Eu3+ foi primeiramente encapsulado na sílica e posteriormente foi adicionado o ligante 2- tenoiltrifluoroacetona (tta). Esse procedimento foi realizado para as sílicas lavada, calcinada e funcionalizada. Uma amostra de sílica funcionalizada foi preparada com a impregnação do complexo já pronto. Todas as amostras foram caracterizadas por espectroscopia luminescente. O estudo espectroscópico foi realizado à temperatura ambiente e os espectros de excitação mostraram a absorção de energia pelo ligante tta na faixa do ultravioleta. Os espectros de emissão mostraram as transições características do íon Eu3+, dos estados de maior energia 5D0 para os de menor energia 7F0-4. Foi observado que a transferência de energia do ligante para o íon Eu3+ foi eficiente. A transição hipersensitiva 5D0→7F2 mostrou o efeito das diferentes superfícies da matriz de sílica. PALAVRAS CHAVE: Sílica mesoporosa, luminescência, európio. / Abstract: MSU-4 type mesoporous sílica has been synthesized with polyoxyethylenesorbitan monolaurate (Tween 20) as structure-directing agent (MTS) as a template and tetraethyl orthosilicate Si(OEt)4 (TEOS) as silica source. The mesoporous structures have a wide application in the luminescence study because of their organization, large surface area, and size of pores. In this work, MSU-4 mesoporous silica was functionalized with 3-amino-propyl-triethoxysilane (APTES) for luminescence applications. Mesoporous silica and amino-functionalized silica was characterized by small-angle X-ray scattering (SAXS), infrared spectroscopy (FT-IR) and nitrogen adsorption/desorption isotherms at 77 K (BET). A luminescent material was prepared by formation of the complex Eu(tta)3 in methanolic medium within the channels of MSU-4 type ordered mesoporous silica. Using simple wet impregnation methods, the europium ion was first encapsulated followed by ligand 2-thenoyltrifluoracetonate (tta) addition. This process it was done for washed, calcined and functionalized mesoporous silica. Analogous one sample of functionalized silica was impregnated with the complex already ready. All samples were characterized by photoluminescence spectroscopy. The spectroscopy studies in room temperature showed the energy absorption of the ligand range ultraviolet in excitation spectra. The emission spectra this materials displayed the typical Eu3+ intra-4f6 lines ascribed to transitions between the 5D0,1 excited states and the ground multiplet (7F0-4). Negligible emission from the organic part of the encapsulated species was observed, indicating that energy transfer from the ligands to the Eu3+ ion was quite efficient. The hypersensitive 5D0→7F2 line showed the mesoporous silica effect in luminescence europium chelate. / Orientador: Marco Antonio Utrera Martines / Coorientador: Gustavo Rocha de Castro / Banca: Cláudio Luiz Carvalho / Banca: Ademir dos Santos / Mestre

Graduation date: 1998

Aerogels are extremely high surface area, low density materials with applications including thermal and acoustic insulators, radiation detectors and cometary dust particle traps. However, their low density and aggregate structure makes them extremely fragile and practically impossible to machine or handle without breaking. This has led to the development of aerogel composites with enhanced mechanical properties through the addition of polymers or surface modifiers. To date, attempts to strengthen aerogels have come with significant increases in density and processing time. Here I will describe our search for a solution to these problems with our invention using methyl cyanoacrylate chemical vapor deposition (CVD) to strengthen silica, aminated silica and bridged polysilsesquioxane aerogels. This approach led to a strength improvement of the composites within hours and the strongest composite prepared had a 100x strength improvement over the precursor aerogel. We also developed the first approach to control the molecular weight of the polymers that reinforce silica aerogels using surface-initiated atom transfer radical polymerization (SI-ATRP). Although PMMA reinforcement of silica aerogels improved the mechanical properties, further strength improvements were achieved by cross-linking the grafted PMMA. Additionally, we developed the first silica aerogels reinforced with polyaniline nanofibers that were strong and electrically conductive. Reinforcing silica aerogels with polyaniline allowed them to be used as a sensor for the detection of protonating and deprotonating gaseous species. Finally we developed a new approach for the synthesis of silica and bridged polysilsesquioxane spheres using a surfactant free synthesis. This approach allowed for the first in-situ incorporation of base sensitive functionalities during the sol-gel polymerization.

Thesis (Ph. D.)--Oregon State University, 2008. / Printout. Includes bibliographical references (leaves 173-191). Also available on the World Wide Web.

Orientador: Renata Marques de Melo Marinho / Coorientador: Tiago Moreira Bastos Campos / Banca: Rubens Nisie Tango / Banca: Getulio de Vasconcelos / Resumo: Neste trabalho avaliou-se o comportamento mecânico e a homogeneidade estrutural de bilaminados cerâmicos com configuração convencional (compressão da zircônia) e bioinspirada (tração da zircônia) com e sem infiltração de sílica. Além disso, determinou-se a distribuição de tensões utilizando a análise de elementos finitos, e avaliou-se o modo de falha e o mecanismo de adesão da interface porcelana/zircônia. Amostras bilaminadas foram confeccionadas com Y-TZP e cerâmica injetável e divididos em 4 grupos (n=30): zircônia sob compressão (T), zircônia infiltrada sob compressão (I), zircônia sob tração (B) e zircônia infiltrada sob tração (BI); para teste da resistência à flexão biaxial. A infiltração por sílica ocorreu pelo método sol-gel. Os dados (MPa) do ensaio mecânico foram avaliados com análise de Weibull (IC 95 %). Análise de elementos finitos utilizou o critério de tensão máxima principal para avaliar a distribuição de tensões nos modelos e seus resultados foram apresentados em forma de figuras e gráficos da tensão máxima principal (TMP). A camada de infiltração foi caracterizada usando DRX e microscopia (MEV, MEV-FEG e EDS). O comportamento da interface foi analisado usando resistência ao risco e dureza. O grupo mais homogêneo estruturalmente foi o BI (m= 9,59). A concentração de tensão na cerâmica feldspática foi menor nos grupos bioinspirados. Houve formação de silicato de zircônia na superfície dos discos de zircônia infiltrados e preenchimento de defeitos superficiais... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study analyzed the mechanical behavior of bilayers using conventional arrangement (leucite ceramic under traction) and a bioinspired arrangement (zirconia under traction) with or without sol-gel silica infiltration, analyze stress distribution using FEA, characterize infiltration layer and observe interfacial behavior. 120 bilayered specimens were produced for biaxial flexural strength testing using Y-TZP and pressed ceramic and divided into 4 groups (n=30): zirconia under compression (T), infiltrated zirconia under compression (I), zirconia under traction (B) and infiltrated zirconia under traction (BI). The zirconia was infiltrated using sol-gel method. The results for the biaxial flexural strength (MPa) were analyzed using Weibull analysis (CI 95 %). Stress distribution within the models were examined using maximum principal stress and the results were presented as graphs and figures. The infiltration layer was characterized using XRD and microscopy (SEM, FEG-SEM and EDS). The interfacial behavior was analyzed using scratch test and micro-hardness indentation. The BI group was the most reliable (m=9.59). The stress distribution in the feldspar ceramic was better for the bioinspired groups. The infiltrated zirconia discs presented zirconia silicate formation on the surface and plugged internal flaws. The traditional zirconia had a better scratch performance compared to the infiltrated zirconia. The interfacial indentation showed that the weakest link of the set is the ... (Complete abstract click electronic access below) / Mestre