No description available.

The adhesion of poly(dimethyl siloxane) (PDMS) to silica substrates was measured by 90 degree peel testing of PDMS strips cast on silica substrates. The objective of this work was to investigate the effects of silica surface chemistry on the adhesion between PDMS and silica substrate. Silica substrates with different surface chemistry were prepared by both chemical modification and physical adsorption. Silane coupling agents were used to provide octyl chains and primary amino groups on the silica surfaces. Also silica surfaces were coated with cetyltrimethylammonium bromide (CTAB), polyvinylamine (PVAm) or poly(N-isopropylacrylamide) (PNIPAM) by physical adsorption. The adhesion samples were prepared by casting Sylgard® 184 silicone elastomers on silica surfaces followed by thermal curing. Water contact angle measurements, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared microscopy (FTIR) were performed to measure the surface properties of the peel test samples. It is believed that hydrogen bonding between siloxane bonds in PDMS and silanol groups on silica substrate contributes to the strong adhesion of PDMS and silica surface. The adhesion forces significantly reduced by the adsorption of PVAm and PNIPAM onto silica surfaces. In addition, the introduction of primary amino groups on silica surface would poison the catalyst during the curing of PDMS, which causes the formation of low crosslinking PDMS in the outer surface and is expected to decline the adhesion force. Lastly, the slightly reduce of adsorbed PVAm (340 kDa) on the silica substrate after peel test is considered to be useful for long-term lubrication. / Thesis / Master of Applied Science (MASc)

<p> This thesis focuses on the use of time-resolved fluorescence anisotropy (TRF A) for the analysis of peptide-silica and protein-silica interactions. Previous studies from our group have shown that strong ionic binding of the cationic probe rhodamine 6G (R6G) to the anionic surface of silica particles in water provides a convenient labeling procedure to study both particle growth kinetics and surface modification by time-resolved fluorescence anisotropy (TRF A). The decays for R6G dispersed in diluted Ludox silica sols usually fit to a sum of picosecond and nanosecond decay components, along with a significant residual anisotropy component. The first objective of my work was to assess the nature of the R6G:silica interaction to determine the origin of the nanosecond decay component, and ultimately validate the model used to fit the TRFA data and gain further insight into the physical meaning of the anisotropy decay parameters. Our results show the origin of the nanosecond decay component ( ¢2) is due to the presence of a subpopulation of small nanoparticles in the Ludox sol. </p> <p> With the correct physical model in place, we have been able use TRFA ofR6G in aqueous Ludox to monitor peptide adsorption onto the silica particles in situ. Steady-state anisotropy and TRF A of R6G in Ludox sols were measured to characterize the extent of the ionic binding of the probe to silica particles in the presence of varying levels of tripeptides of varying charge, including Lys-Trp-Lys (KWK), N-acetylated Lys-Trp-Lys (Ac-KWK), Glu-Trp-Glu (EWE) and N-acetylated Glu-Trp-Glu (Ac-EWE). R6G showed significant decreases in anisotropy in the presence of cationic peptides, consistent with the addition of cationic peptides blocking the adsorption of the dye to the silica surface. The study shows that the competitive binding method can be used to assess the binding of various biologically relevant compounds onto silica surfaces, and demonstrates the potential of TRF A for probing peptide: silica and protein: silica interactions. </p> <p> We have also extended the application of TRF A to monitor protein adsorption onto plain and modified silica particles using a recently reported cationic long-lifetime quinolinium dye, CG437, which strongly binds to anionic silica particles through electrostatic interactions. In this case, alterations in the rotational correlation time of Ludox particles resulting from increases in the diameter of the rotating body upon binding of protein to the silica surface were monitored. The study shows that TRFA analysis of long-lived cationic probes such as CG437 can provide an effective method to investigate interactions between proteins and modified silica surfaces, extending the utility of the TRF A method. </p> / Thesis / Master of Science (MSc)

A great deal of interest has been dawn on the colloidal chemistry based semiconductor nanocrysallites, also known as quantum dots (QDs). Because of the strong quantum confinement, quantum dots have unique size-dependent optical properties, which are much more superior to the conventional organic fluorescence materials. In addition, strong chemical resistant makes inorganic semiconductor QDs ideal candidate for next-generation of bio-labels and drug delivery vehicles. This report presents a user friendly approach to synthesize high quality biocompatible CdSe QDs in aqueous solution. Size of the dots can be controlled by adjusting the temperature, pH of the solution, and ratio of the precursors. A thin CdS layer was grown on CdSe QDs, forming a CdSe/CdS core/shell structure, to improve the photoluminescence. In order to use these QDs in-vivo, a more chemically robust coating, silica, was grown on the core/shell structure QD. The optical properties of the QDs were characterized by absorption and photoluminescence spectra. X-ray diffraction and transmission electron microscopy were conducted to verify the QDs composition and structure. / Ph. D.

Porous silica-based nanocomposites are promising ceramics, as they exhibit high specific surface area, highly porous network, and a surface that can be easily functionalized. This dissertation describes the results of a study on the formation and properties of porous silica nanoparticle-based composites, using techniques of freeze casting and sintering. Kaolinite platelets and silica nanorods were added into the nanoparticle system, and their effects on modifying the porous microstructures and physical properties were investigated. During freeze casting, homogeneous microstructures with highly interconnected porosity are fabricated. Kaolinite addition results in large and more interconnected pores, while added silica nanorods cause a pore morphology evolution from circular to elongated spherical pores with increasing aspect ratio. The specific surface areas (area/mass) of the particles are conserved during freeze casting and values for the resulting composites can be accurately predicted using the area and mass of the components assuming conservation of area. Both kaolinite platelets and silica nanorods effectively improved the strength of the freeze cast green composites as they distribute any applied stress over a larger portion of the sample. Upon sintering, added kaolinite is found to modify the sintering behavior of the silica nanoparticles and a transitioning interfacial phase is identified when sintering temperature is above 1250 °C. This new phase contributes to the further enhancement of strength and this strengthening effect depends on composition and initial solids loading. After sintering at 1250 °C for 1 h, a ceramic containing 10 vol% kaolinite and 8 vol% silica has a maximum strength while maintaining a ~69% porosity. The kaolinite-silica composites with lower solids loading exhibit faster sintering (e.g. larger shrinkage, more extensive thickening of the pore walls), which, in turn, results in a rapid increase in mechanical strength. Based on the understanding of the composite properties and the underlying principles, a novel method for creating nanocomposites with precisely controllable specific surface area is developed. With repeated nanoparticle suspension infiltration, freeze drying, and sintering, the specific surface area can be varied from less than one to well over 100 m2/g, demonstrating potential application as liquid membranes. / Ph. D.

M.S.

Reliable sensing and monitoring systems based on optical fibers operating at high temperatures and in harsh environments are of high demand. One of the limitations of such systems is the devitrification of the fused silica based core and cladding glass at elevated temperatures. Crystallites can nucleate on the surface of the cladding and grow into the core. The formation of these crystalline flaws in the optical fiber causes stress concentration and extrinsic optical scattering and in addition leads to decreased mechanical properties and reduced optical stability. Commercial optical fibers of different compositions and core-cladding design were characterized in this study with respect to crystallization rate under various conditions. The optical stability was monitored with an optical spectrum analyzer. The crystallites were characterized with SEM and optical microscopy. The activation energies of crystallization for High OH and Low OH multimode fibers were estimated by measuring the crystal growth rate at different temperatures. The residual stress resulting from the formation of the crystals, which can lead to decreased mechanical performance of the fibers, was characterized with polarized light optical microscopy. The influence of water vapor in the atmosphere on the crystallization rate was determined. The features induced in the attenuation spectra were consistent with hydroxyl (OH) absorption peak. Spectral features such as thermal emission and hydroxyl absorption bands are discussed. The results obtained in this study can be used for selecting optical fibers for high temperature applications. / Master of Science / Reliable sensing and monitoring systems based on glass optical fibers operating at high temperatures and in harsh environments are in high demand. One of the limitations of such systems is the tendency of glass material to crystallize at elevated temperatures. Crystallites can nucleate on the surface of the fiber and grow inwards, impairing the optical and mechanical properties of the optical fiber. The formation of these crystalline flaws in the optical fiber can decrease the mechanical strength by causing stress concentrations and leading to formation of cracks, and reduce optical stability by causing light to scatter from the crystals. Commercial optical fibers of different compositions and geometry were characterized in this study with respect to crystal growth rate under various conditions, such as different temperatures (400-1350 °C), and different atmospheres (laboratory air and water vapor). The effect of crystals was demonstrated with respect to optical and mechanical performance. The results obtained in this study can be used for selecting optical fibers for high temperature applications.

In this thesis we used atomic force microscopy (AFM) to investigate systematically the behaviour of both electrostatically stabilised silica and sterically stabilised polystyrene (PS) colloidal systems on freshly cleaved mica substrates. For the silica colloidal nanoparticles we explored the effect of colloidal suspension concentration, particle size, and different application techniques on both the adsorption behaviour and subsequent structuring of the particles. For the PS colloidal nanoparticles we explored concentration effects and experimented with both dip-coating and droplet application techniques. We showed that silica nanoparticles adsorbed onto mica via irreversible adsorption that possessed lateral mobility due to the weak attraction between the nanoparticles and the substrate, facilitating subsequent capillary structuring of the nanoparticles during drying. We associated the effects of volume fraction with Debye screening, and kinetics effects with particle size and volume fraction. We also successfully imaged a partially dried film and showed the role of convective/capillary forces in the structuring of the nanoparticles. Studies with variations in particle size generated a number of different topography structures; with dewetting phenomena observed for 10 nm nanoparticles and the formation of crystalline structures for 100 nm nanoparticles. Spin coating techniques were used to produce even larger crystalline structures of nanoparticles. Size dependent ordering occurred for low concentration samples due to the polydispersity of the colloidal suspension. We showed that acceleration can affect interparticle spacing. We also studied the role of rotational speed on the crystallinity of the particle configurations and showed how fine tuning of rotational speed can generate large scale monolayer crystalline formations of nanoparticles.

Nenhuma / Materiais mesoporosos ordenados tipo SBA-16 possuem uma rede de canais e poros de tamanho bem definido na escala nanométrica, com estrutura cúbica, elevada área superficial (400 1000 m2.g-1) e tamanho de poros usualmente em torno de 2 a 30 nm. Essa estrutura de poros torna esses materiais apropriados para incorporar e liberar uma grande variedade de moléculas na sua matriz. Dentre os diversos tipos de materiais SBA, o SBA-16 é considerado uma mesoestrutura muito interessante devido ao fato de possuir um ordenamento de mesoporos cúbico tridimensional correspondente ao grupo especial Im3m, podendo ser um material promissor para várias aplicações. Os materiais mesoporosos podem sofrer diversas modificações na sua superfície, devido à presença dos grupos silanóis, podendo produzir um material com uma funcionalidade direcionada. Neste trabalho, estudou-se a síntese e caracterização do material SBA-16 puro e após o processo de funcionalização para avaliar sua aplicação como sistema de liberação controlada de um fármaco modelo. O processo de modificação da superfície foi realizado pelo método pós-síntese, ou seja, após o obter o material SBA-16, esse passou por um segundo processo para se obter as amostras funcionalizadas. A caracterização do SBA-16 puro e funcionalizado foi feita por análise elementar (CHN), Espectroscopia na Região do Infravermelho com Transformada de Fourier (FTIR), Análise Termogravimétrica (TG), Adsorção de Nitrogênio, Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão (MET), Espalhamento de Raios X a Baixos Ângulos (SAXS), e Ressonância Magnética Nuclear (RMN). Por meio da técnica de espectroscopia de absorção na região do infravermelho, foi possível observar, a partir dos espectros das amostras funcionalizadas, bandas características das vibrações da rede de sílica, bem como bandas referentes às vibrações dos grupos alquilas ancorados na estrutura da sílica. A presença do fármaco atenolol no material mesoporoso e nas amostras funcionalizadas também pode ser confirmada por meio das medidas de FTIR. A estabilidade térmica e as degradações que ocorrem nos componentes puros, bem como nas amostras modificadas na superfície, foram investigadas e estabelecidas pela análise termogravimétrica. Por meio da TG foi possível quantificar a presença dos grupos orgânicos ancorados nesse material. A presença dos grupos orgânicos conduziu a alterações na estrutura do material final, com a diminuição da área superficial e volume de poros. Porém, a distribuição de poros se mostrou semelhante em todas as amostras. Os resultados de MEV, MET e SAXS do SBA-16 e das amostras funcionalizadas revelaram uma estrutura bem ordenada de mesoporos, característica intrínseca desses materiais. Por meio das medidas de ressonância magnética nuclear de 29Si e 13C de estado sólido (RMN-MAS) nas amostras funcionalizadas, foi possível caracterizar e avaliar a forma de ligação desses grupos orgânicos na matriz de sílica. Através do ensaio de liberação, foi possível avaliar a quantidade de atenolol incorporado e verificar o comportamento da liberação desse nas amostras sintetizadas. Com os resultados de citotoxicidade foi possível determinar a viabilidade celular, obtendo-se resultados satisfatórios para uma futura aplicação clínica desse material. / Type ordered mesoporous materials SBA-16 have a network of channels and well defined pore size in nanometer scale. Cubic structure has a high surface area (400 - 1000m2.g-1) and pore size is usually around 20 to 30 nm. This porous structure makes these materials appropriate to incorporate and release a large variety of molecules in the matrix. Among these SBA-type silica materials, SBA-16 is considered a very interesting mesostructure due to the its 3D cubic arrangement of mesopores corresponding to the Im3m space group, a promising material for a large range of applications. The mesoporous materials may undergo several changes in its surface due to the presence of silanol groups, which can produce a material with a targeted feature. The materials were characterized by elemental analysis (CHN), Fourier Transform Infrared Spectroscopy (FTIR), Nitrogen Adsorption, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Small Angle X Ray Scattering (SAXS), Nuclear Magnetic Resonance (RMN), and Thermal Analysis. Through the FTIR analysis technique, it was possible to observe characteristic bands of the silica vibrations, as well as vibrations bands due the presence of alkyl groups anchored into the silica structure. The presence of the atenolol in the mesoporous material and functionalised samples was also confirmed by FTIR. The thermal stability and the degradation of the surface modified samples were determined by thermogravimetry. The incorporation of the organic groups into the mesoporous silica led to a significant change in the structural properties of the system, with the decrease of the specific surface area and pore volume, but the pore size distribuition was similar in all samples. The results obtained by SEM, TEM and SAXS for the samples reveal a well-defined cubic arrangement of uniform mesoporous structure, intrinsic characteristic of these materials. By measuring nuclear magnetic resonance of 29Si and 13C solid state (MAS-NMR) in the functionalized samples, it was possible to characterize and measure the extent of binding of organic groups in the silica matrix. Through the release assay was possible to evaluate the amount of embedded atenolol and verify the behavior of the drug release from the synthesized samples. Considering the results of cytotoxicity, it was possible to determine cell viability by obtaining satisfactory results for future clinical application of this material.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Materiais mesoporosos têm despertado um interesse cada vez maior na comunidade científica, devido à singularidade das suas propriedades, o que os tornam materiais promissores para serem empregados em processos de adsorção, catálise, nanotecnologia e aplicações eletrônicas. Dentre os diversos materiais da série de sílica mesoporosa, destaca-se a família SBAn. Os materiais SBA-16 e SBA-15 se sobressaem em diversos estudos devido às suas diferentes morfologias, tamanho de poros uniformes, elevada área superficial e elevada densidade de grupos silanois na sua superfície. Estas características conferem aos materiais a possibilidade de modificação superficial e imobilização de diversos agentes tais como enzimas para aplicação em biocatálise. O desenvolvimento de técnicas de imobilização de enzimas em nanopartículas de sílica SBAn pode resultar em melhorias do seu desempenho catalítico, reduzir a sua inativação e melhorar a retenção da atividade catalítica por um maior período de tempo. No presente trabalho, diferentes tipos de nanopartículas de sílica SBAn foram sintetizadas e funcionalizadas com 3-amino-propil-triethoxysilane (APTES). As amostras foram caracterizadas por técnicas de Espectroscopia na Região do Infravermelho com Transformada de Fourier (FTIR), Adsorção de Nitrogênio (BET), Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão (TEM), Espalhamento de Raios X a Baixos Ângulos (SAXS), Análise Elementar (CHN) e Análise Termogravimétrica (TG). Foi avaliado o processo de imobilização de lipase de pâncreas do porco (PPL) por adsorção nos suportes sólidos das diferentes nanopartículas de SBAn puras e funcionalizadas, através de reação de hidrólise com o substrato caprilato p-nitrofenila determinados através da técnica de UV-Vis. Foram investigados os diferentes tipos de sílica SBAn e a influência da morfologia no processo de imobilização de lipase (PPL). Os resultados mostraram que a enzima (PPL) foi imobilizada com sucesso em canais de SBAn mesoporosos e que amostra tem um grande potencial para aplicações em biotecnologia. / Mesoporous materials have attracted an increasing interest in the scientific community because of the uniqueness of their properties, which make them promising materials to be employed in the process of adsorption, catalysis, nanotechnology, electronics applications. The mesoporous materials may be chemically manipulated by varying the surfactant and some parameters such as temperature and concentration of the synthesis, which influence the morphology and particle size. Many studies have been developed in the creation of stable materials with well-defined arrangements hexagonal, cubic, lamellar and tetragonal. Among the various materials, the series family of mesoporous silica, highlight the SBAn. These materials are very attractive due to its properties, such as high surface areas and a uniform mesopore size with ordered pore size distribution and readily controlled. The SBA-16 and SBA-15 materials stand out due to their different morphologies and wide application. In this study, different types of nano-silica particles SBAn were synthesized and functionalized with 3-amino-propyl-triethoxysilane (APTES). The samples were characterized by techniques of Fourier Transform Infrared (FTIR), nitrogen adsorption (BET), scanning electron microscopy (SEM), Transmission Electron Microscopy (TEM), Small Angle X- Ray Scattering (SAXS), Elemental Analysis (CHN) and Thermogravimetric Analysis (TG). The immobilization process by adsorption on solid support matrices SBAn silica nanoparticles by hydrolysis reaction with the substrate p-nitropheniyl caprylate determined by UV-VIS technique was evaluated. The different types of silica SBAn and its influence on morphology and functionalization in the process of immobilization of PPL were investigated. The results showed that the enzyme porcine pancreatic lipase (PPL) was successfully immobilized on mesoporous SBAn channels.