Orientadores: Lucia Helena Innocentini Mei, Marcos Akira D'Ávila / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T02:05:21Z (GMT). No. of bitstreams: 1 Bizarria_MariaTrindadeMarques_D.pdf: 4483205 bytes, checksum: 44e9caae2b1e4e2bd5569681573ba911 (MD5) Previous issue date: 2012 / Resumo: A obtenção de nanofibras de polímeros biocompatíveis, baseadas em quitosana, bem como a montagem de equipamento capaz de produzi-las, foi o principal objeto deste trabalho. Com este propósito, buscou-se de início reunir os dispositivos eletrônicos e mecânicos indispensáveis à prática da eletrofiação e um equipamento básico, de baixo custo, mas funcional foi construído. Com base na literatura, o ácido acético glacial a 90% em água deionizada foi o solvente utilizado para preparo das soluções de quitosana. Para viabilizar o processo da produção das nanofibras pela técnica da eletrofiação utilizaram-se blendas de soluções de quitosana com soluções de outros polímeros biocompatíveis em vez de soluções de quitosana pura. Assim, blendas de soluções de quitosana com soluções aquosas do poli(óxido de etileno) - PEO , bem como, com soluções aquosas de Poli(álcool vinílico) - PVA, em diversas proporções, foram eletrofiadas. O Poli(óxido de etileno) mostrou superior desempenho, como auxiliar na fiação da quitosana, permitindo a obtenção de fibras com até 80% de quitosana, e com diâmetros inferiores àqueles obtidos com as blendas de soluções de quitosana/PVA. A adição de um eletrólito (NaCl) às soluções blendas de quitosana/PEO proporcionou um processo fácil ininterrupto, sendo assim, buscou-se um melhor entendimento sobre as propriedades das soluções da quitosana e do PEO que norteiam comportamentos mais ou menos favoráveis ao processo da eletrofiação, caracterizando-se essas soluções através de estudos de viscosidade, de medidas de tensão superficial e de condutividade elétrica. A morfologia das fibras obtidas foi caracterizada por microscopia eletrônica de varredura (MEV) e, as propriedades térmicas, das membranas nanoestruturadas resultantes da eletrofiação das soluções de Quitosana/PEO, foram avaliadas por análise termogravimétrica (TGA) e calorimetria diferencial exploratória (DSC). A biocompatibilidade das membranas com teor de quitosana mais elevado (80% quitosana/20% PEO) foi avaliada através de testes de citotoxicidade in vitro, biocompatibilidade in vivo e adesão e crescimento celular in vitro. Adicionalmente, foram conduzidos experimentos visando avaliar o desempenho destas mesmas membranas como carreadoras de fármacos sendo que, a incorporação de nanopartículas de prata (AgNPs), bem como de digluconato de clorexidina apresentaram resultados promissores / Abstract: The development of biocompatible polymer nanofibers based on chitosan and the design and assembly of equipment capable of producing them were the main objectives of this work. For this purpose, the basic electronic and mechanical devices were obtained and a low-cost functional electrospinning setup was built. Based on the literature, glacial acetic acid with concentration of 90% in deionized water was the solvent used to prepare the chitosan solutions. In order to enable the nanofiber production by electrospinning, blends of chitosan solutions with other biocompatible polymers were used instead of pure chitosan solutions. Thus, blends of chitosan solutions with aqueous solutions of poly (ethylene oxide) PEO as well as with aqueous solutions of poly (vinyl alcohol) PVA, in various proportions, were electrospun. The PEO presented superior performance as an aid to obtain chitosan fibers, resulting in fibers with up to 80% of chitosan, and with smaller diameters than those obtained with solutions of blends of chitosan / PVA. The addition of an electrolyte (NaCl) to the chitosan/PEO solution blends has provided an easy and uninterrupted process. Thus, to obtain a better understanding about the properties of chitosan and PEO solutions that lead to more or less favorable behaviors to the electrospinning process, these solutions were characterized by performing viscosity studies and measurements of surface tension and electrical conductivity. The morphology of the fibers was evaluated by scanning electron microscopy (SEM) and the thermal properties of nanostructured membranes resulting from electrospinning of chitosan/PEO solutions were evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).The biocompatibility of the higher-content-chitosan membranes (80%chitosan /20% PEO) was evaluated by tests of in vitro cytotoxicity, in vivo biocompatibility and in vitro cell adhesion and growth. In addition, experiments were conducted to evaluate the performance of the same membrane as a carrier of drugs. In this way, the incorporation of silver nanoparticles (AgNPs) and chlorhexidine digluconate showed promising results / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

Orientador: Claudio Longo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T05:20:37Z (GMT). No. of bitstreams: 1 Oliveira_BrunoHondade_M.pdf: 1755012 bytes, checksum: c581e51105ddf9e770994460e5171e65 (MD5) Previous issue date: 2011 / Resumo: As células fotoeletroquímica de TiO2/corante, que convertem energia solar em elétrica, são constituídas por fotoeletrodo de TiO2 modificado com um corante, contra-eletrodo de Pt e um eletrólito contendo o par redox I/ I3. Neste trabalho, investigaram-se eletrólitos constituídos por NaI/I2 dissolvido em uma matriz polimérica de poli(óxido de etileno), PEO, contendo 10% (em massa) dos polifluoretos polivinilideno (PVdF) e polivinilideno hexafluoro-propileno, PVdF-HFP. Inicialmente, averiguou-se que um eletrólito constituído por 14% de NaI ( em relação à massa de PEO) em PEO/PVdF-HFP apresentou melhor desempenho em uma célula solar que um eletrólito similar em matriz PEO/PVdF. Determinou-se então, para eletrólitos de PEO/PVdF-HFP, a condutividade iônica em função da concentração de NaI para filmes depositados entre eletrodos bloqueantes de aço. O valor máximo de condutividade, 0,3 mScm, foi obtido para o eletrólito contendo mNaI/mPEO = 20%. Em uma célula simétrica, constituída por dois eletrodos de Pt, os voltamogramas cíclicos obtidos para este eletrólito apresentaram picos bem definidos, indicando a reversibilidade do par redox neste eletrólito. A adição de 10% (em massa) de PVdF-HFP proporciona característica amorfa à matriz polimérica, o que garante alta mobilidade iônica. As células solares preparadas com este eletrólito (área ativa de 0,5 cm) apresentaram, no 1° dia, valores médios de corrente de curto circuito de 3,9 mA cm e potencial de circuito aberto, VOC, de 0,6V e eficiência de conversão 1,1% sob irradiação de um simulador solar (120mWcm, 27°C). Através de medidas de espectroscopia de impedância eletroquímica sob irradiação (no Voc, ± 10 mV), observou-se baixa resistência em série e estimou-se o coeficiente de difusão das espécies redox no sistema em D= 3.10 cms. As curvas corrente-potencial foram determinadas durante 30 dias consecutivos; sendo observada estável depois de 15 dias e uma diminuição de 60% de sua eficiência inicial / Abstract: Dye-sensitized solar cell convert solar energy in electricity, are made up nanoporous TiO2 electrode modified by a Ru-complex dye, Pt counter electrode and an electrolyte containing the redox couple I/ I3. This dissertation was to investigate electrolytes consisting of NaI/I2 dissolved in a polymer matrix of poly (ethylene oxide), PEO, containing 10% (by weight) of polyvinylidene polyvinylidene (PVDF) and polyvinylidene Hexafluorosilicic propylene, PVdF-HFP. Initially, it was found that electrolyte content 14% of NaI (mNaI/mPEO) in PEO / PVdF-HFP performed better on a solar cell array in a similar electrolyte PEO / PVdF. It was determined then to electrolyte PEO / PVdF-HFP, the ionic conductivity as a function of NaI concentration for films deposited between steel blocking electrodes. The maximum conductivity, 0.3 mScm, was obtained for he electrolyte containing mNaI / mPEO = 20%. In a symmetric cell, consisting of two Pt electrodes, the cyclic voltammograms obtained for this electrolyte showed well defined peaks, indicating the reversibility of the redox couple in electrolyte. The addition of 10% (in mass) of PVdF-HFP provides the characteristic amorphous polymer matrix, which ensures high ion mobility. Solar cells prepared with this electrolyte (active area 0.5 cm) presented on first day, mean values of short circuit current of 3.9 mA cm and open circuit potential, VOC of 0.6 V and conversion efficiency of 1.1% under irradiation of a solar simulator (120 mWcm, 27°C). Through measures electrochemical impedance spectroscopy under irradiation (in VOC, ± 10 mV), there was low resistance in series and estimated the diffusion coefficient of redox species in the system at D = 3.10 cms. The current-potential curves were determined for 30 consecutive days, being observed stable after 15 days and a decrease of 60% of its initial efficiency / Mestrado / Físico-Química / Mestre em Química

No description available.

The electrospinning process of polymer solutions is affected by many different parameters that can be divided into solution parameters, process parameters, and ambient parameters. This study is focused on characteristics of a polymer and its solution, which are ranging into the solution parameters. The aim of this study is to compare poly(ethylene oxide) characteristics in the relation to electrospinning of hyaluronic acid, to find the difference between them using available analytic, thermic and spectral methods, and to define the influence of properties on polymeric solutions behavior during electrospinning. It was find that poly(ethylene oxides) obtained from two different sources behave differently in an electrostatic field, although their molar mass is declared as the same. It was also confirmed that the electrospinning process of polymeric solutions is affected mainly by their viscosity and conductivity. This two properties are determined especially by the molar mass of polymer and also by the content of impurities or content of some another polymer during electrospinning of mixed solution.

No description available.

<p> High molecular weight poly(ethylene oxide) (PEO) is used in conjunction with a cofactor such as phenol formaldehyde resin (PFR) as flocculants for newsprint manufacture. The objectives of the work described in this thesis were to prepare flocculants superior to PEO and to determine the flocculation mechanism. A series of novel comb copolymers consisting of a polyacrylamide backbone with short pendant poly(ethylene glycol) (PEG) chains was prepared and characterized. Additionally, polymerization conversion curves and reactivity ratios were measured. An interesting finding was that the reactivity of the macromonomer in free radical copolymerization decreased with PEG chain length. </p> <p> Flocculation results with both model latex dispersions and commercial wood pulp suspensions showed that copolymer chain length was the most important variable ; molecular weights greater than 3 million were required for good flocculation. On the other hand, the PEG pendant chains could be as short as 9 ether repeat units. Also, only 1 to 2 PEG chains for every 100 acrylamide backbone moieties were required. </p> <p> No published flocculation mechanisms could predict all the behaviors of the PEO or copolymer system. A new mechanism called complex bridging was proposed. According to this mechanism PEO or copolymer chains aggregate in the presence of cofactor to form colloidally dispersed polymer complex which heteroflocculates with the colloidal particles. </p> <p> Given in this work is the first explanation of the requirement for extremely high PEO or copolymer molecular weights for flocculation. It is proposed that polymer chains with molecular weights less than 106 collapse in the presence of PFR to an inactive precipitate before flocculation can occur whereas complexes based on very high molecular weight PEO collapse slowly enough to permit flocculation. </p> <p> Published mechanistic studies are hindered by the fact that PFR has poorly defined structures. It is shown for the first time in this work that welldefined, linear, poly(p-vinyl phenol) (PVPh) is an effective cofactor. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.

Well-defined heterobifunctional homopolyethers and amphiphilic block copolyethers containing a variety of functionalities were designed, synthesized, and characterized via GPC and 1H NMR. These have included controlled molecular weight cholesterol-PEO-OH, mono- and trivinylsilyl-PEO-OH, monovinylsilyl-PEO-PPO-OH, monovinylsilyl-PEO-PPO-PEO-OH, maleimide-PEO-OH, stearyl alcohol-PEO-OH, propargyl alcohol-PEO-OH, trivinylsilyl-PPO-OH, trivinylsilyl-PPO-PEO-OH, and benzyl alcohol-initiated poly(allyl glycidyl ether)-OH. The focus of polymers utilized in this study involved the mono- and trivinylsilyl polyethers. The vinylsilyl endgroups on these materials were functionalized with various bifunctional thiols through free radical addition of SH groups across the vinylsilyl double bonds. The resultant end-functional polyethers were adsorbed onto magnetite nanoparticles and the stabilities of the polymer-magnetite complexes were compared as a function of the type of anchoring moiety and the number of anchoring moieties per chain. Anchoring chemistries investigated in this work included carboxylates, alkylammonium ions, and zwitterionic phosphonates. The anchor group-magnetite bond stability was investigated in water and phosphate buffered saline (PBS). Through these studies, the zwitterionic phosphonate group was shown to be a better anchoring group for magnetite than either carboxylate or ammonium ions. Tri-zwitterionic phosphonate anchor groups provided stability of the complexes in PBS for a broad range of polymer loadings. Thus, investigations into the stability of polyether-magnetite complexes in PBS focused on hydrophilic zwitterionic phosphonate-PEO-OH and amphiphilic zwitterionic phosphonate-PPO-b-PEO-OH oligomer coatings on the surface of magnetite. Superparamagnetic magnetite nanoparticles are of interest as potential contrast-enhancement agents for MRI imaging. Thus, transverse NMR relaxivities of these complexes were studied as a function of chemical composition and nanostructure size and compared to commercial contrast agents. The amphiphilic polyether-magnetite nanoparticles were shown to be stable in both aqueous media as well as physiological media and have much higher transverse relaxation values, r2, than those of commercial contrast agents and other materials in the literature. / Ph. D.

The composition and stability of polymer-magnetite complexes is essential for their use as a treatment for retinal detachment, for drug targeting and delivery, and for use as a MRI contrast agent. This work outlines a general methodology to design well-defined, stable polymer-magnetite complexes. Colloidal modeling was developed and validated to describe polymer brush extension from the magnetite core. This allowed for the observation of deviations from expected behavior as well as the precise control of polymer-particle complex size. Application of the modified Derjaguin-Verwey-Landau-Overbeek (DLVO) theory allowed the determination of the polymer loading and molecular weight necessary to sterically stabilize primary magnetite particles. Anchoring of polyethers to the magnetite nanoparticle surface was examined using three different types of anchor groups: carboxylic acid, ammonium, and zwitterionic phosphonate. As assessed by dynamic light scattering (DLS), the zwitterionic phosphonate group provided far more robust anchoring than either the carboxylic acid or ammonium anchor groups, which was attributed to an extremely strong interaction between the phosphonate anchor and the magnetite surface. Coverage of the magnetite surface by the anchor group was found to be a critical design variable for the stability of the zwitterionic phosphonate groups, and the use of a tri-zwitterionic phosphonate anchor provided stability in phosphate buffered saline (PBS) for a large range of polymer loadings. Incorporation of an amphiphlic poly(propylene oxide)-b-poly(ethyelene oxide) (PPO-b-PEO) diblock copolymer attached to the magnetite surface was examined through colloidal modeling and DLS. The relaxivity of the complexes was related to aggregation behavior observed through DLS. This indicated the presence of a hydrophobic interaction between the PPO layers of neighboring complexes. When this interaction was large enough, the complexes exhibited an increased relaxivity and cellular uptake. Thus, we have developed a methodology that allows for design of polymer-magnetite complexes with controlled sizes (within 8% of predicted values). Application of this methodology incorporated with modified DLVO theory aids in the design of colloidally stable complexes with minimum polymer loading. Finally, determination of an anchor group stable in the presence of phosphate salts at all magnetite loadings allows for the design of materials with minimum polymer loadings in biological systems. / Ph. D.

This dissertation focuses on synthesis and characterization of graft and block copolymers containing carboxylate or phosphonate anions that are potential candidates for biomedical applications such as drug delivery and dental adhesives. Ammonium bisdiethylphosphonate (meth)acrylate and acrylamide phosphonate monomers were synthesized based on aza-Michael addition reactions. Free radical copolymerizations of these monomers with an acrylate-functional poly(ethylene oxide) (PEO) macromonomer produced graft copolymers. Quantitative deprotection of the alkylphosphonate groups afforded graft copolymers with zwitterionic ammonium bisphosphonate or anionic phosphonate backbones and PEO grafts. The zwitterionic copolymers spontaneously assembled into aggregates in aqueous media. The anionic copolymers formed aggregates in DMF and DMSO, while only small amounts of aggregates were present in copolymer/methanol or copolymer/water solutions. Binding capabilities of the acrylamide phosphonic acids were investigated through interactions with hydroxyapatite. Previously our group has prepared poly(ethylene oxide)-b-poly(acrylic acid) (PEO-b-PAA) copolymers and used these polymers as carriers for both MRI imaging agents and cationic drugs. To enhance the capabilities of those carriers in tracking and crosslinking, we have designed, synthesized and characterized amine functionalized PEO-b-PAA copolymers. First, heterobifunctional poly(ethylene oxide) (PEO) with three different molecular weights were synthesized. Modification on one of these afforded a PEO macroinitiator with a bromide on one end and a protected amine on the other end. ATRP polymerization of tert-butyl acrylate (tBuA) in the presence of this initiator and a copper (I) bromide (CuBr) catalyst yielded a diblock copolymer. The copolymer was deprotected by reaction with trifluoroacetic acid (TFA) and formed an amine terminated H2N-PEO-b-PAA. Recently our group has utilized the novel ammonium bisdiethylphosphonate (meth)acrylate and acrylamide phosphonate copolymers to incorporate Carboplatin. The resulting complexes exhibited excellent anticancer activity against MCF-7 breast cancer cells which might be related to ligand exchange of the dicarboxylate group of Carboplatin with the phosphonic acid moieties in the copolymer. Hence, complexation of small-molecule phosphonic acids with Carboplatin was investigated. Three compounds, vinylphosphonic acid, 3-hydroxypropyl ammonium bisphosphonic acid and 2-hydroxyethyl ammonium phosphonic acid were complexed with Carboplatin under acidic and neutral conditions. Covalent bonding of these acids to carboplatin was only observed under acidic pH. The covalently bonded percentage was 17%, 37% and 34%, respectively. More in-depth investigation was of great importance to further understand this complexation behavior. / Ph. D.