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

Orientadores: André Luiz Barboza Formiga, Maria Isabel Felisberti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T16:07:14Z (GMT). No. of bitstreams: 1 Jannuzzi_SergioAugustoVenturinelli_M.pdf: 35610656 bytes, checksum: f2dffeb8cf285399ac0996a04b2601a7 (MD5) Previous issue date: 2011 / Resumo: O presente trabalho ocupa-se da síntese, caracterização e aplicação de um material híbrido orgânico-inorgânico em que o bloco orgânico é o polímero poli(4-vinilpiridina) e o bloco inorgânico é o pentacianoferrato(II) de sódio. A primeira parte trata da influência do polímero nas propriedades do complexo, e vice-versa. A segunda parte ilustra a aplicação do metalopolímero na produção de estruturas análogas ao azul da Prússia (AP) pela reação de Fe com as unidades pentacianoferrato. A banda de transferência de carga metal-ligante do pentacianoferrato do metalopolímero em solução desloca-se para energias menores na medida em que aumenta a fração de meros livres da cadeia polimérica, indicando que a fração do bloco orgânico modula a polaridade do ambiente químico do complexo. Por outro lado, a crescente quantidade de complexo ligado às cadeias poliméricas aumenta viscosidade das soluções de metalopolímeros, evidenciando que o pentacianoferrato expande o novelo macromolecular. Estruturas tipo azul da Prússia sintetizadas a partir do metalopolímero exibem elevada estabilidade coloidal quando comparadas aos compostos isentos de polímero e apresentam banda de intervalência em menores energias do que o frequentemente reportado para esse tipo de estrutura, provavelmente em virtude do envolvimento das partículas de AP pelo polímero / Abstract: This work comprises the synthesis, characterization and application of a hybrid organic-inorganic metallopolymer, in which the organic block is the polymer poly(4-vinylpyridine) and the inorganic block is the complex sodium pentacyanoferrate(II). The first part presents the influence of the polymer on the properties of the complex and vice-versa. The second part illustrates an application of the metallopolymer on the production of Prussian blue (AP) analogs based on the reaction of Fe with the pentacyanoferrate moieties. The metal-to-ligand charge transfer band of the polymer-bound pentacyanoferrate in solution shifts towards lower energies whereas the free monomers fraction arises. It indicates that the organic block fraction tunes the polarity of the pentacyanoferrate chemical environment. On the other side, the increasing fraction of complex bound to the polymer chain increases the metallopolymer solution viscosities. This is an evidence that the pentacyanoferrate expands the macromolecular coil. Prussian blue-type structures synthesized from metallopolymers exhibit enhanced colloidal stability when compared to the polymer-free compounds. They also present intervalence bands at lower energies than those frequentlly reported for this type of inorganic structure. The reason is probably the polymer wrapping of the particles / Mestrado / Quimica Inorganica / Mestre em Química

A method for assaying poly (ADP-ribose) polymerase (PADPRP) activity in lymphocytes of systemic lupus erythematosus (SLE) patients has been developed. Using this method, PADPRP activity has been studied in lymphocytes from 15 patients and 13 controls. The mean activity in SLE lymphocytes was significantly lower than that in controls and 60% of the SLE patients demonstrated activities below the minimum of the control population. Possible mechanisms for this altered metabolism were investigated. The Km app of PADPRP for NAD; size distribution, branch frequency, and rates of turnover of polymers; competition for substrate; and number of PADPRP molecules were studied. The data demonstrated that SLE lymphocytes have a decreased synthetic capacity rather than alterations in the substrate or in turnover of the product.

La synthèse de nanogels par voie directe est étudiée par la copolymérisationradicalaire réticulante contrôlée par le cobalt (CMRCcP) d’un monomère monovinylique et d’unréticulant divinylique. La synthèse de nanogels globulaires a été réalisée en utilisant unsystème de co-monomères soit neutres (acétate de vinyle et adiapte de divinyle) soit liquidesioniques. Le contrôle de la polymérisation est vérifié dans tous les cas, les liaisons C-Cosituées aux extrémités des chaînes polymères ont été réactivées, afin de former des nanogelsde « seconde-génération ». Dans le cas de monomères liquides ioniques, différents contreanionsont été utilisés afin de jouer sur l’hydrophilie des co-monomères : la CMRCcP dubromure de N-vinyl-3-ethyl imidazolium (VEtImBr) et du bromure de 1,13-divinyl-3-decyldiimidazolium (DVImBr) a été réalisée dans l’eau, à 30 °C, pour former des nanogelspoly(VEtImbr-co-DVImBr) hydrophiles. Les propriétés antibactériennes de ces nanogels ontété étudiées.Les pendants hydrophobes de ces nanogels à base de PILs ont été synthétisés via laCMRCcP directe, dans l’acétate d’éthyle, de co-monomères contenant des contre-anionsbis(trifluromethanesulfonyl)imide (NTf2-). La capacité à former des surfaces poreusesordonnées de ces nanogels hydrophobes poly(VEtImNTf2-co-DVImNTf2) a été examinée, ainsique leur conductivité ioniques en films minces.Des copolymérisations ‘mixtes’ ont également été étudiées, dans l’optique de formerdifférentes architectures nanogels en utilisant des co-monomères ayant des réactivités trèsdifférentes. / The syntheses of globular nanogels were first investigated under mild conditions,using a mono- and a divinyl co-monomer with similar reactivities. CMRCcP was implementedon either neutral (vinyl acetate (VAc) and divinyl adipate (DVA)) co-monomers, or ionic liquidco-monomers. Control over each polymerization was ascertained, and dormant cobaltcarbonchain-ends could be re-activated to form “second-generation” nanogels. CMRCcP ofN-vinyl-3-ethyl imidazolium bromide (VEtImBr) and 1,13-divinyl-3-decyl diimidazoliumbromide (DVImBr) was achieved in water at 30 °C, leading to hydrophilic poly(VEtImBr-co-DVImBr) nanogels. The antibacterial activity of these cross-linked structures wasinvestigated. The hydrophobic pendants of these PIL-based nanogels were synthesized viadirect CMRCcP in ethyl acetate, using bis(trifluromethanesulfonyl)imide (NTf2-) counteranions. An array of these poly(VEtImNTf2-co-DVImNTf2) nanogels was then investigated aspossible coatings for porous patterned surfaces, and their ionic conductivity assessed.Different cross-linked architecture were approached, using a mono- and a divinyl comonomersof completely different reactivities.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14942号 / 工博第3169号 / 新制||工||1475(附属図書館) / 27380 / UT51-2009-M856 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 小澤 文幸, 教授 大江 浩一, 教授 中村 正治 / 学位規則第4条第1項該当

Conductive polymers are also known as "organic metals" due to their semiconducting properties. They are found in a wide range of applications in the field of organic electronics. However, the growing number of experimental works is not widely supported with theoretical calculations. Hence, the field of conductive polymers is experiencing lack of understanding of mechanisms occurring in the polymers. In this PhD thesis, the aim is to increase understanding of conductive polymers by performing theoretical calculations.        The polymers poly(3,4-ethylenedioxythiophene) (PEDOT) together with its selenium (PEDOS) and tellurium (PEDOTe) derivatives, poly(p-phenylene) (PPP) and naphthobischalcogenadiazoles (NXz) were studied. Several computational methods were applied for analysis of mentioned structures, including density functional theory (DFT), tight-binding modelling (TB), and Car-Parrinello molecular dynamics (CPMD) calculations. The combination of CPMD and DFT calculations was applied to investigate the PEDOT, PEDOS and PEDOTe. The polymers were studied using four different functionals in order to investigate the full picture of structural changes, electronic and optical properties. Temperature effects were studied using molecular dynamics simulations. Wide statistics for structural and molecular orbitals analysis were collected.         The TB method was employed for PPP. The formation and motion of the excitations, polarons and bipolarons, along the polymer backbone was investigated in presence of electric and magnetic fields. The influence of non-magnetic and magnetic impurities was determined.        The extended π-conjugated structures of NXz were computed using B3LYP and ωB97XD functionals in combination with the 6-31+G(d) basis set. Here, the structural changes caused by polaron formation were analyzed. The combined analysis of densities of states and absorption spectra was used for understanding of the charge transition. / <p>QC 20170928</p>

La pollution des sols par les solvants chlorés constitue un problème environnemental majeur avec des conséquences importantes sur la pollution des eaux, et donc, sur l'utilisation de cette ressource essentielle. Parmi les procédés de traitement, l'oxydation in situ apparaît comme une alternative viable, de grand intérêt, en ce qui concerne le traitement des polluants en phase organique (DNAPL). L'objectif principal de ce travail a été d'analyser les limitations cinétiques contrôlant l'oxydation du percloroethylène (PCE) en phase DNAPL avec des solutions de KMnO4, et cela dans des conditions diverses d'opération : concentration d'oxydant, aire interfaciale, mode de contact et phases en contact, principalement. Au préalable à cette étude, des méthodes analytiques ont été développées, notamment pour l'analyse du PCE en phase aqueuse. Dans un système homogène à température constante et en phase aqueuse la vitesse de la réaction a été mesurée et une loi cinétique a été proposée, valable dans une gamme étendue des compositions. Puis la réaction a été étudiée en système polyphasique, L/L (réacteur agité) et S/L/L (milieu poreux). La démarche consistait à déterminer dans des expériences sans oxydant (dites de dissolution) le coefficient de transfert de matière caractéristique du système, puis de l'appliquer au calcul du nombre de Hatta. Ce critère adimensionnel apporte des informations sur la localisation de la réaction, et donc sur la vitesse relative des phénomènes de transfert et réaction en série. Dans les conditions expérimentales étudiées plusieurs régimes de fonctionnement, caractérisés par des valeurs du critère de Hatta allant de 0,03 à 3,6 ont été observés. Par conséquent, le processus d'oxydation peut être contrôlé soit par le transfert soit par la réaction, et cela que l'on soit en réacteur agité qu'en milieu poreux. / The pollution of soils with chlorinated solvents is a major environmental problem with important consequences for the water contamination, hence for the utilisation of this essential resource. Among the treatment processes, in situ chemical oxidation appears as a viable alternative, of great interest for the treatment of dense non aqueous phase liquids (DNAPL). The aim of this work was to analyse the kinetic limitations controlling perchloroethylene (PCE) oxidation in dense non aqueous phase liquid with permanganate (KMnO4) solutions and that in diverse operational conditions: oxidant concentration, interfacial area, contact mode and contact phases, mainly. First, analytical methods were developed, especially for PCE analyse in aqueous phase. In a homogeneous system, at constant temperature and in aqueous phase, the real reaction rate was measured and a kinetic low was proposed, applicable to a large range of compositions. Then, the reaction was studied in a multiphase system, L/L (batch reactor) and S/L/L (porous media). The procedure consisted in establishing the mass transfer coefficient of the system in experiments without oxidant (so-called of dissolution), then applying it to the identification of Hatta number. This dimensionless criterion brings us information about the reaction location and consequently, about the relative rate of the global process. In the studied experimental conditions, several operational regimes, characterised by Hatta values in a range from 0.03 to 3.6, were observed. Therefore, the oxidation process can be controlled either by transfer or by reaction and that even in batch reactor and in porous media

Common biodegradable polyesters such as poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA) and poly(ε-caprolactone) (PCL) are used as drug delivery vehicles for tissue regenerative applications. However, they are typically bioinert, with drug loading limitations. Polymerizing the active agent or precursor into its respective biodegradable polymer would control drug loading via molar ratios of drug to initiator used for synthesis. Simvastatin was chosen due to its favorable anti-inflammatory, angiogenic, and osteogenic properties. In addition, its lactone ring lends itself to ring-opening polymerization and, consequently, the synthesis of poly(simvastatin) with controlled simvastatin release. Simvastatin was first polymerized with a 5kDa methyl-terminated poly(ethylene glycol) (mPEG) initiator and catalyzed via stannous octoate to form poly(simvastatin)-block-poly(ethylene glycol). Molecular weights ranged from 9.5kDa, with a polydispersity index (PDI) of 1.1 at 150 °C, to 75kDa with a PDI of 6.9 at 250 °C. First-order propagation rates were seen. Infrared spectroscopy showed carboxylic and methyl ether stretches unique to simvastatin and mPEG in the copolymer, respectively. Slow degradation was seen in neutral and alkaline conditions, with simvastatin, simvastatin-incorporated macromolecules, and mPEG identified as degradation products. Alternatively, triazabicyclodecene (TBD) was used to mediate simvastatin polymerization. A lower temperature of 150°C led to successful polymerization using 5kDa mPEG, compared to at least 200 °C via stannous octoate. TBD was also successful for reactions using 2 or 0.55kDa mPEG. The biodegradability of poly(simvastatin)-block-poly(ethylene glycol) via TBD improved, losing twice more mass in phosphate-buffered saline, pH 7.4, than the copolymer synthesized via stannous octoate. Release rates of three different copolymers synthesized demonstrated tunable simvastatin release. To further modulate degradation, poly(simvastatin)-block-poly(ethylene glycol) was blended with 5, 2, or 0.55kDa mPEG-initiated PLA copolymers. The blends showed a compressive elastic modulus ranging from 26 to 44MPa, within the magnitude of trabecular bone (approximately 50MPa). Tunability in mass loss and release was also seen due to varied ratios of incorporated PLA copolymers. Lastly, copolymer degradation byproducts inhibited HMG-CoA reductase and showed possible enhancement of osteoblastic activity in vitro. A pilot study using a rodent calvarial onlay model showed tolerability of the polymers and potential for long-term evaluations of bioactivity. Poly(simvastatin) may be useful in regenerative applications.

Les thérapeutiques individualisées et ciblées se développent actuellement, les formes galéniques évoluent donc en parallèle pour contrôler la libération des principes actifs (PA) et les conduire au plus proche des sites d’intérêts. Les formes orales solides représentent les formulations galéniques les plus utilisées, faciles d’emploi, indolores et réduisant le risque d’infection. Lors de leur conception, il est aussi possible de moduler la libération du PA.Deux approches sont étudiées dans ce manuscrit, l’une correspond au ciblage de la libération d’un PA vers son site d’action thérapeutique qui est le colon, la seconde consiste à contrôler la libération du PA pour maintenir une concentration constante, minimiser les effets indésirables et les périodes de présence de concentrations sub-thérapeutiques au niveau du site d’action.Première approche :Les traitements des Maladies Inflammatoires Chroniques de l’Intestin (MICI) peuvent être significativement améliorées par une libération localisée du PA. Une des approches est l’utilisation d’enrobages composés de polysaccharides dégradés par les enzymes sécrétées par la microflore colique. Mais l’absence d’une méthode in vitro reproductible simulant les conditions physiologiques du colon et l’impact potentiel des traitements antibiotiques associées qui pourraient affecter la quantité et la qualité des bactéries présentes et des enzymes sécrétées est un obstacle à sa mise au point. L’objectif de l’étude était d’effectuer un screening de polysaccharides ayant un intérêt dans le développement de nouvelles formulations à libération colique. Après cette sélection, la libération des formulations retenues ont été évaluées par une méthode utilisant des selles de patients atteints de MICI traités ou non par antibiothérapie. Enfin, l’utilisation de mélanges bactériens pour un éventuel remplacement de l’utilisation de selles fraiches a été évaluée.Seconde approche : Les formes orales enrobées présentent un grand potentiel pour la libération contrôlée de PA. Néanmoins, il est difficile d’obtenir une libération à vitesse constante avec ce type de formulation. Ceci est généralement dû au rôle prédominant du transport de masse par diffusion, ce qui entraine, avec le temps, une diminution de la concentration en PA au cœur du système, donc une réduction du gradient de concentration qui est la force motrice de la libération du PA. Ce type de cinétique de libération peut être inapproprié pour un traitement médicamenteux sûr et efficace. Malgré l’importance pratique de ce défi crucial de formulation, étonnamment, peu de stratégies efficaces sont connues. Dans cette étude, une nouvelle approche, basée sur une succession de couches de PA et de polymères (initialement dépourvu de PA) présentant une distribution initiale de PA non homogène, associé à un effet de temps de latence et à une diffusion partielle initiale à travers le noyau de la minigranule. Des variations de type, de quantité, d’épaisseur et de séquence des couches de PA et de polymères ont été testées. Un système assez simple composé de quatre couches (deux couches de PA et deux couches de polymère) permettait d’aboutir à une libération relativement constante durant 8h. / Individualized and targeted therapies are currently developed, therefore the dosage forms move in parallel to control the drug release and drive it nearest to interest sites. Solid oral dosage forms are the pharmaceutical formulations the most common, easy to use, painless and reducing the infectious risk. In these formulation designs, it is also possible to adjust the drug release.Two approaches are discussed in this manuscript, the first one targets the drug release to the therapeutic site of action which is the colon, and the second one consists on controlling the drug release to maintain a constant concentration, minimize side effects and periods of presence of sub-therapeutic concentrations at the site of action.The first approach:The treatment of colonic disease like Inflammatory Bowel Diseases (IBD), can be significantly improved via local drug delivery. One approach is to use polysaccharide coatings, which are degraded by enzymes secreted by the colonic microflora. However, the lack of a reliable in vitro test simulating conditions in a living colon and the potential impact of associated antibiotic treatments that could affect the quality and quantity of bacteria and enzymes secreted is an obstacle to its development. The aim of the study was to perform a screening of polysaccharides suitable for the development of new colonic release formulations. After this selection, the drug release of selected formulations were evaluated by a method using the stools of IBD patients treated or not with antibiotics. Finally, the use of bacterial mixtures substituting fresh fecal samples has been evaluated.The second approach: Coated pellets offer a great potential for controlling drug delivery systems. However, constant drug release rates are difficult to achieve with this type of dosage forms if the drug is freely water-soluble. This is because diffusional mass transport generally plays a major role and with time the drug concentration within the system decreases, resulting in decreased concentration gradients, which are the driving forces for drug release. This type of release kinetics might be inappropriate for an efficient and safe drug treatment. Despite the great practical importance of this potentially crucial formulation challenge, surprisingly little is yet known about efficient formulations. In this study, a novel approach is presented based on sequential layers of drug and polymer (initially free of drug) to provide a non-homogeneous initial drug distribution, combined with lag-time effects and partial initial drug diffusion towards the pellet’s core. By changing the type, number, thickness and sequence of the drug and polymer layers, a rather simple 4 layers system (2 drug and 2 polymer layers) allowed an about constant drug release during 8 h.

The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide. The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism. / Science, Faculty of / Chemistry, Department of / Graduate