abstract: Bacteriophage provide high specificity to bacteria; receiving interest in various applications and have been used as target recognition tools in designing bioactive surfaces. Several current immobilization strategies to detect and capture bacteriophage require non-deliverable bioactive substrates or modifying the chemistry of the phage, procedures that are labor intensive and can damage the integrity of the virus. The aim of this research was to develop the framework to physisorb and chemisorb T4 coliphage on varied sized functionalized silica particles while retaining its infectivity. First, silica surface modification, silanization, altered pristine silica colloids to positively, amine coated silica. The phages remain infective to their host bacteria while adsorbed on the surface of the silica particles. It is reported that the number of infective phage bound to the silica is enhanced by the immobilization method. It was determined that covalent attachment yielded 106 PFU/ml while electrostatic attachment resulted in 105 PFU/ml. / Dissertation/Thesis / Masters Thesis Civil and Environmental Engineering 2017

Orientador: Carlos Lenz Cesar / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-11T19:07:11Z (GMT). No. of bitstreams: 1 Almeida_DiogoBurigo_M.pdf: 7702783 bytes, checksum: a49d734c4420be66d8e50ab224c6225f (MD5) Previous issue date: 2008 / Resumo: Pontos quânticos são nanocristais com diâmetros na escala de 10 a 100 Å. Por serem tão pequenos, elétrons e buracos sofrem um forte confinamento quântico, modificando as propriedades ópticas desses materiais. Seu uso como marcadores fluorescentes vem se mostrado de notável importância, pois os usados até então são, em geral, compostos orgânicos muito sensíveis à luz e ao meio ao qual são submetidos, além de serem citotóxicos e possuírem uma banda de absorção restrita para cada tipo de marcador. O ponto quântico por si só tem uma eficiência quântica pequena (menor que 20%) visto que, por tratar-se de uma estrutura nanoscópica, a razão entre sua área superficial e seu volume é muito grande, fazendo com que seus defeitos de superfície (dangling bonds) exerçam papel fundamental no processo de emissão, criando sub-níveis de energia, aumentando a banda de emissão do ponto quântico e a sua perda de energia. Além disto nanocristais de emissão no visível são constituídos de calcogenetos de cádmio, o que os torna muito tóxicos às estruturas biológicas envolvidas, caso este seja dissociado. A solução para estes dois problemas proposta e desenvolvida no nosso trabalho foi a encapagem do ponto quântico com uma camada de material inerte e resistente, no nosso caso o dióxido de silício. Neste trabalho de mestrado desenvolvemos o estudo de rotas simples para obtenção de pontos quânticos coloidais de CdSe e CdTe encapados com sílica, aumentando assim a estabilidade das partículas no meio e cuja principal aplicação foi seu uso como marcadores celulares fluorescentes. Dividimos esta dissertação basicamente em quatro partes: O capítulo 2 será devotado para o estudo tanto da modelagem do confinamento que o ponto quântico exerce sobre os elétrons e buracos quanto para as cinéticas da reação de formação das partículas coloidais. O terceiro capítulo foca os métodos de sínteses utilizadas para o trabalho, dando ênfase ao processo de silanização. No quarto capítulo apresentamos os resultados das medidas de caracterização e suas interpretações além de aplicações. E finalmente, o último capítulo apresenta nossas conclusões e perspectivas futuras para nosso trabalho / Abstract: Quantum dots are nanocrystals with diameters between 10 and 100 Å. Because they are so small, electrons and holes suffer a strong quantum confinement, modifying the optical properties of these materials. Their use as fluorescent markers have become very important, because the ones used until then, are, in general, organic compounds very sensitive to light and the media they are insert in. Besides, they are toxic and have a narrow and specific absorption band for each marker. The quantum dot itself has low quantum efficiency (less than 20%) and, how it is a nanoscopic structure the ration between its superficial area and volume is high, so the dangling bonds on the surface exert a fundamental hole in the emission process, creating energy sub-levels, increasing the emission band of the quantum dot and its energy loss. Besides nanocrystals that have emission in the visible band are usually made of cadmium calcogenides, what makes them harmful for live structures, if the atoms are dissociated from de quantum dot. The solutions for these two problems proposed and developed in our work was the quantum dot coating with an inert and resistant material, in our case, silica. In this masters work we developed the study of simple silanizations routes in order to obtain silica coated CdSe and CdSe quantum dots, and so increasing the particles environmental stability for mainly using them as fluorescent cell markers. We divided this dissertation basically in four parts: the chapter two is about the study of the quantum confinement and colloidal reactions kinetics. The third chapter deals with the synthesis methods as well the silanizations ones. In the fourth chapter we show the results obtained with its discussions. And the last chapter is devoted to the conclusion and perspectives of this work / Mestrado / Física / Mestre em Física

Silicon Nanowire-based biosensors owe their sensitivity to the large surface area to volume ratio of the nanowires. However, presently they have only been shown to detect specific bio-markers in low-salt buffer environments. The first part of this thesis presents a pertinent next step in the evolution of these sensors by presenting the specific detection of a target analyte (NT-ProBNP) in a physiologically relevant solution such as serum. By fabrication of the nanowires down to widths of 60 nm, choosing appropriate design parameters, optimization of the silicon surface functionalization recipe and using a reduced gate oxide thickness of 5 nm; these sensors are shown to detect the NT-ProBNP bio-marker down to 2ng/ml in serum. The observed high background noise in the measured response of the sensor is discussed and removed experimentally by the addition of an extra microfabrication step to employ a differential measurement scheme. It is also shown how the modulation of the local charge density via external static electric fields (applied by on-chip patterned electrodes) pushes the sensitivity threshold by more than an order of magnitude. These demonstrations bring the silicon nanowire-based biosensor platform one step closer to being realized for point-of-care (POC) applications. In the second half of the thesis, it is demonstrated how silicon micromechanical piezoelectric resonators could be tasked to provide wireless power to such POC bio-systems. At present most sensing and actuation platforms, especially in the implantable format, are powered either via onboard battery packs which are large and need periodic replacement or are powered wirelessly through magnetic induction, which requires a proximately located external charging coil. Using energy harnessed from electric fields at distances over a meter; comprehensive distance, orientation, and power dependence for these first-generation devices is presented. The distance response is non-monotonic and anomalous due to multi-path interferences, reflections and low directivity of the power receiver. This issue is studied and evaluated using COMSOL Multiphysics simulations. It is shown that the efficiency of these devices initially evaluated at 3% may be enhanced up to 15% by accessing higher frequency modes.

Functionalized silica materials are synthesized for various environmental applications. The overall objective is functionalization with sulfur-containing moieties for mercury sorption and as a platform for nanoparticle synthesis. The first objective is quantifying this functionalization for various silica platforms. The second objective is development of effective mercury sorbents, for both aqueous mercury and elemental mercury vapor. Third, those sorbents are incorporated into mixed matrix membranes (MMM) for aqueous mercury sorption. Fourth, functionalized silica materials are developed as platforms for the synthesis of reactive metal nanoparticles (NP) for the degradation of trichloroethylene. Thiol-functionalized silica is used as a sorbent for aqueous mercury, and a novel functionalized material (thiol-functionalized silica shell surrounding a carbon core) has been developed for this application. Total capacity and kinetics of aqueous mercury sorption were determined. The silica-coated carbon was functionalized with thiol and sulfonate moieties for regeneration under mild conditions. Finally, the sorbent particles were incorporated into polysulfone to form a mixed matrix membrane (MMM) for toxic metal capture under convective-flow conditions. High loadings (up to 50% particles, base particles of ~80 nm) were achieved in the MMM. The particles are well-dispersed which can lower mass transfer resistance to the sorption sites. The MMM also imparts several practical advantages such as ease of sorbent handling. Silica functionalized with tetrasulfide silane is used for mercury vapor sorption. Sorption kinetics and dynamic capacity depend upon pore structures of the functionalized material. The particles are thermally stable and exhibit a glass transition in the tetrasulfide silane coating, with high total sorption capacity achieved by addition of copper sulfate. Temperature effects on mercury sorption indicate a chemisorptive mechanism. Silica particles functionalized with sulfonate moieties were used as a platform for the synthesis of dispersed iron nanoparticles. These NP are applied for degradation of trichloroethylene (TCE), a persistent, toxic, and widespread pollutant. The particles were stabilized against agglomeration. Natural product reducing agents, such as ascorbic acid, adsorb to the particle surface and can protect against oxidation. These particles were demonstrated for the reductive as well as oxidative degradation of TCE.

Les fonctions organiques du corps humain sont liées à des constants biologiques. Variations de ces constantes induisent divers états pathologiques. Parmi ces constantes, le pH constitue le cœur de ces travaux de thèse. Chez les êtres vivants, les fonctions biologiques dépendent de constant acides ou alcalines. En fait, l’action d’une protéine dépend du pH du milieu environnant. Une valeur inadéquate du pH rend les protéines inactives ce qui est délétère pour l’organisme. Il existe donc un besoin pour des capteurs de pH qui puissant être utilisés dans le corps humain pour des applications cliniques (échelle macroscopique), sur des cellules en culture pour des recherches en biologie (échelle mesoscopique) et pour étudier les échanges ioniques au niveau des membranes cellulaires pour des travaux plus fondamentaux (échelle microscopique). Parmi le large éventail de technologies potentiellement candidates pour ces applications, la mesure de pH par fibre optique exploitant la fluorescence permet d’être adaptée aux trois échelles dimensionnelles susnommées. Ce manuscrit de thèse adresse des contraintes par l’étude de capteurs fluorescents à fibre optique utilisant deux types d’indicateur de pH: les SNARF et la fluorescéine. En parallèle de ces développements expérimentaux, des descriptions mathématiques des propriétés de fluorescence de ces deux indicateurs sont proposées. Ces descriptions permettent de progresser vers une mesure du pH sans calibration / Organic functions of the human body are linked to biological constants. Variations of these constants induce pathological troubles. Among these constants, the pH is the central subject of this PhD work. In living beings, biological functions are related to either acid or alkaline constants. Indeed, the action of a protein depends on the surrounding pH. An inadequate value of the pH makes the proteins non active which is deleterious for the organism. There exist a need for pH sensors which can be used in the human body for clinical applications (macroscopic scale), on cells in culture for biology researches (mesoscopic scale) or at a cell membrane level for more fundamental studies (microscopic scale). Among the wide range of technologies potentially useful for these applications, fiber optic fluorescence pH sensing offers the possibility to be adapted to the three above mentioned dimensional scales. This PhD dissertation addresses these constraints by studying fluorescence fiber optics pH sensors using two kind of pH indicators: SNARF and fluorescein. Together with these experimental studies, mathematical descriptions of the fluorescence properties of these indicators are proposed. They allow progressing towards calibration free pH sensing.

Aluminum alloys are widely used materials in the aircraft industry due to their high specific strength and durability. The natural corrosion resistance of aluminum can be improved through an electrochemical anodizing process. Due to recent restrictions in the use of chromic acid with toxic hexavalent chromium as electrolyte, the industry has shifted towards the use of the functional comparable tartaric sulfuric acid (TSA). TSA anodizing provides a porous alumina layer with good corrosion resistance, yet there is a desire to tune the process to fit other purposes. For instance, ice accretion to aircraft surfaces implies a safety risk and reduced energy efficiency. Due to insufficient active anti-icing systems, aircraft manufacturers are in the search for passive anti-acing materials. The ice adhesion properties of a material are thought to be affected by wettability. In turn, the wettability is affected by the morphology of the alumina influenced by the anodizing conditions. Herein, the effects of the anodizing voltage, electrolyte temperature and anodizing time on the morphology and wettability of TSA-anodized aluminum alloy 2024-T3 were studied by scanning electron microscopy (SEM) and contact angle (CA) measurements. The morphology in relation to wettability and ice adhesion strength as well as the use of posttreatments such as hydrothermal sealing and silanization was investigated. SEM images show a clear influence by the anodizing conditions on the porosity, interpore distance and pore diameter of the porous alumina. The morphology has influence on the wettability although the relationship needs further investigation. A superhydrophobic surface obtained by silanization of a surface anodized at high voltage characterized by a rod-like morphology has potential as a passive anti-icing surface. Future work may include additional polishing pretreatments, testing of additional parameters, investigating the CA hysteresis and roll-off angle as well as measuring the adhesion strength of high-impact ice. By tuning the morphology of sustainable anodic coatings, the research area is one step closer to implementing passive anti-icing materials in aircrafts.

Complex engineered nanoparticles (CENPs) are being used on various applications. Their properties are different from those of neat nanoparticles. The dissertation explores these differences from four aspects: 1) Modify carbon nanomaterials’ inert surfaces and investigate the effect on thermal and rheological behavior of their dispersions; 2) Generate self-assembly bi-layer structure of oxide nanoparticles via surface modification; 3) Study interaction between lysozyme and different surface-charged ceria nanoparticles; 4) Investigate the biodistribution and transformations of CENPs in biological media. An environment-friendly surface modification was developed to modify surfaces of carbon nanomaterials for increasing their affinity to non-polar fluid. It can offset formation of agglomerates in dispersions. Less agglomerates change thermal conductivity and rheological behavior. One combined model, considering shape factor, was built to fit non-linear enhancement on thermal conductivity with volume fraction of nanoparticles. Constructing bi-layer structure of oxide nanoparticles with different refractive index was crucial for optical thin films. Silanization was used to transform relatively hydrophilic surface of oxide nanoparticles to hydrophobic surface via attaching alkane chains. The self-assembly separation of these nanoparticles can form bi-layer structure in single deposition process since neat nanoparticles keep in hydrophilic monomer while surface-modified nanoparticles settled down. The adsorption behaviors of lysozyme, one protein with net positive charge, on different surface-charged ceria nanoparticles were investigated. The adsorption isotherm curves were fitted with the Toth and Sips equations satisfactorily. The heterogeneity parameters suggest the surface charge predominate adsorption on negatively charged ceria while lateral effect predominate adsorption on positively charged ceria. The local site energy distributions were also estimated. The 26Al-labeled nanoalumina coated by 14C-labeled citrate was synthesized and its dispersion was infused intravenously into rat. The Accelerator Mass Spectrometer (AMS) was used to measure isotopes in dosing material and tissues. The ratio of coating and core in liver was slightly less than dosing material while the ratios in brain and bone are much higher than dosing material. It may suggest that some citrate coating dissociated from nanoalumina’s surface, entered metabolic cycles, and then redistributed to other organs.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-06-25T14:52:33Z No. of bitstreams: 1 PATRÍCIA COSTA FERNANDES DE MENEZES - TESE (PPGCEMat) 2015.pdf: 20736985 bytes, checksum: 6d5bf08cc6b3770e921031c7b7dd8006 (MD5) / Made available in DSpace on 2018-06-25T14:52:33Z (GMT). No. of bitstreams: 1 PATRÍCIA COSTA FERNANDES DE MENEZES - TESE (PPGCEMat) 2015.pdf: 20736985 bytes, checksum: 6d5bf08cc6b3770e921031c7b7dd8006 (MD5) Previous issue date: 2015-01-14 / Capes / A tecnologia Stealth é a capacidade de navios, aeronaves e submarinos tornarem-se invisíveis à detecção de radares. Para isso, se faz necessário o uso de Materiais Absorvedores de Radiação Eletromagnética – MARE que atuem de forma efetiva no bloqueio da radiação emitida pelos radares. Neste contexto, o objetivo desta pesquisa foi obter um compósito de matriz polimérica de borracha de silicone e carga de ferrita NiZn nanométrica em diferentes concentrações, visando sua utilização como um MARE. A carga foi sintetizada por reação de combustão e os compósitos foram obtidos com concentrações de carga variando entre 16 e 20 g e quantidade de silicone fixa de 20g. Visando investigar a melhor interação entre a carga e a matriz, a carga foi silanizada com 3-aminopropiltrietoxissilano e incorporada apenas ao compósito na concentração de 20:20 de carga:silicone. As técnicas de Difração de Raios-X (DRX), Espectroscopia na Região do Infravermelho por Transformada de Fourrier (FTIR), Microscopia de Força Atômica (AFM), Microscopia eletrônica de Varredura (MEV), Medidas Magnéticas e Eletromagnéticas foram utilizadas para caracterizar a carga e os compósitos. Observou-se que a carga apresentou a fase cristalina do espinélio inverso, com tamanho de partícula nanométrico, com característica de um material magnético mole com valores de absorção de -15,2 dB na faixa de 3 a 4 GHz. Todos os compósitos apresentaram características de MARE com valores de absorção variando de -5 a -17,5 dB na faixa de 3 e 6 GHz. De forma geral, verificou-se que o aumento do teor da carga no compósito dificultou a dispersão e introduziu defeitos volumétricos do tipo poros e aglomerados da carga, porém, não influenciou nos parâmetros magnéticos. A silanização não causou alterações significativas nas propriedades da ferrita, porém contribuiu efetivamente para uma melhor interação com a matriz, resultando diretamente no compósito com o melhor valor de absorção, -14 dB na faixa de 6 GHz, indicando ser o mais promissor para a aplicação como MARE. / Define the Stealth technology as the ability of ships, aircraft and submarines become invisible to radar detection. For this, it is necessary to use materials that effectively reduce this probe, this field that can stand out the use of Radiation Absorbing Materials Electromagnetic - RAME. The objective of this research was to obtain a polymer matrix composite silicone rubber and NiZn ferrite load with different concentrations and better dispersion, for their use as a MARE. The composites were obtained with concentrations varying load between 16 and 20 g of NiZn ferrite synthesized by combustion. To improve the interaction between the cargo and the matrix, it has been silanized with 3 aminopropyltriethoxysilane silane agent and incorporated into a composite. The techniques of X-ray diffraction (XRD), Infrared Spectroscopy in the region by Fourier transform (FTIR), Atomic Force Microscopy (AFM), scanning electron microscopy (SEM), Magnetic and Electromagnetic measurements were used to characterize the load and composite. It was noted that the load presented to the inverse spinel crystalline phase with nanometer particle size with characteristics of a soft magnetic material with 15.2 dB absorption values in the range 3 to 4 GHz. Silanization caused no change significant feature in the ferrite, but contributed effectively for better interaction with the matrix, resulting directly in the composite with the best absorption values, -14 dB at 6 GHz range, indicating that the most promising for application as RAME. For other composites was found that increasing the filler content provided processing difficulties which resulted in the formation of agglomerates and will not influence the magnetic parameters.

The current study discusses the preparation and long-term performance of polymer composites used for various purposes under different ageing conditions. The first part deals with the preparation and characterization of polymer nanocomposites based on poly(ethylene-co-butyl acrylate) (EBA–13 and EBA–28 with 13 and 28 wt % butyl acrylate, respectively) and 2–12 wt % (0.5–3 vol %) of aluminum oxide nanoparticles (two types with different specific surface areas and different hydroxyl-group concentrations; uncoated and coated with, respectively, octyltriethoxysilane and aminopropyltriethoxysilane). The nanocomposite with EBA–13 showed better overall nanoparticle dispersion while EBA–28 resulted in poor dispersion, probably due to insufficiently high shear forces acting during extrusion mixing which were unable to break down nanoparticle agglomerates. The activity of hindered phenolic antioxidant (0.2 wt%) in all EBA nanocomposites was assessed by determining the oxidation induction time using DSC. The composites containing uncoated aluminium oxide nanoparticles showed a much shorter initial OIT than the pristine polymer with the same initial concentration of antioxidant, indicating adsorption of antioxidant onto the nanoparticle surfaces. Composites containing coated nanoparticles showed a significantly smaller decrease in the initial OIT, suggesting the replacement of hydroxyl groups with organic silane tails, decreasing the concentration of available adsorption sites on the nanoparticle surfaces. The decrease in OIT with increasing ageing time in dry air at 90 °C of the nanocomposites was slower than that of the unfilled pristine polymer, suggesting a slow release of antioxidant from adsorption sites. The EBA nanocomposites exposed to liquid water at 90°C showed faster decrease of OIT than samples exposed to dry or humid air. The migration rate of antioxidant was controlled by the boundary conditions in the case of ageing in humid air and liquid water. The antioxidant diffusivity was lower for the composites containing uncoated ND than for the composites containing ND coated with octyltriethoxysilane or aminopropyltriethoxysilane. The migration and chemical consumption of deltamethrin DM, (synthetic pyrethroid) and synergist piperonyl butoxide from molded polyethylene sheets was also studied. Deltamethrin and piperonyl butoxide are often used for food  storage and insect control purposes. DM showed no signs of crystallization and remained in a liquid state after being cooled to room temperature. Exposure of polyethylene compound sheets to liquid water (at 80 &amp; 95 °C), caused degradation and hydrolysis of the ester bond in the DM, present in the prepared material, and generated species containing hydroxyl groups. Liquid chromatography and infrared spectroscopy showed a significant migration of the active species in liquid water, whereas in air at 80 °C (60 and 80 %RH) the loss of DM and PBO was negligible over 30 days. The long-term performance of medium-density polyethylene stabilized with six different phenolic antioxidants (0.1 wt%) in aqueous chlorinated media at 70 °C was studied. The results were compared with data for previously studied solutions of antioxidants in squalane (a liquid, low molar mass analogue of polyethylene). A linear relationship was established between the time to reach antioxidant depletion in polyethylene tape samples and the time in squalane samples. Infrared spectroscopy and scanning electron microscopy of drawn samples revealed the onset of surface oxidation and surface embrittlement in tape samples exposed beyond the time for antioxidant depletion. / <p>QC 20121109</p> / Cable insulation materials / Loss of deltamethrin and pipronyl butoxide from polyethylene / long-term performance of polyethylene in chlorine dioxide water

<p>The newfound capability of creating moisture sensitive interference multilayered thin films (MLTFs) comprising microfibrillated cellulose and polymers has not previously been possible to implement on surfaces other than silicon wafer strips. Being able to incorporate interference MLTFs on fibre-based materials would introduce the possibility for new applications within authentication, sensing and customer attraction for the paper and packaging industry. By using trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane we were able to hydrophobically modify silicon substrates, enabling interference MLTF lift-off and thus the creation of free-standing MLTFs of approximately 400 nm thickness. Contact dried MLTFs approximately 250 nm thick, were successfully transferred to copy- and filter paper as well as to cellulose-based dialysis membranes. We can also report on the successful synthesis of interference MLTFs directly on a fibre composite material and on aluminium. Initial tests of a method to quantify the pull-off conditions of the MLTFs from the fluorinated surfaces using the Micro Adhesion Measurement Apparatus showed promising results.</p>