Ce travail est consacré à l’étude du comportement photochimique d’un encapsulant multifonctionnel de cellules photovoltaïques organiques (CPO) dont la finalité est d’augmenter à la fois la durée de vie et le rendement de conversion des cellules. L’étude rapportée dans ce manuscrit porte sur le développement d’un revêtement permettant la conversion lumineuse du rayonnement UV solaire, ce dernier étant un facteur important de dégradation des CPO à base de P3HT et ne contribuant que faiblement à la conversion photovoltaïque. Dans un premier temps cette étude a porté sur l’élaboration d’une couche de conversion à partir d’une matrice polymère en EVA et d’une charge luminescente inorganique (SrAl2O4 : Eu2+, Dy3+). Dans un second temps, l’évolution des propriétés physiques et chimiques de cette couche de conversion sous irradiation à des longueurs d’onde supérieures à 300 nm a été étudiée. La présence des charges s’est révélée être un facteur pro-dégradant des films composites, sans pour autant que le mécanisme de dégradation du polymère ne soit affecté. L’étude des conditions de propagation de la lumière dans les films diffusants par l’application de la théorie de Mie a mis en évidence une possible augmentation du trajet optique des photons dans certains films composites. Ce phénomène pourrait contribuer à expliquer l’origine du comportement photochimique particulier des films étudiés. C’est finalement une preuve de concept qui a été recherchée pour l’utilisation d’un revêtement multifonctionnel pour l’amélioration et la conservation des propriétés de conversion d’une CPO à base de P3HT. / This work is devoted to the study of the photochemical behavior of a multifunctional coating dedicated to the encapsulation of organic solar cells (OSC), elaborated with the aim of improving both the lifetime of the cells and their efficiency. The study reported in this manuscript focuses on the development of a coating allowing the conversion of UV sunlight, this last greatly damaging P3HT based OSC and poorly contributing to the photovoltaic conversion. A composite film was then elaborated by incorporating an inorganic luminescent filler (SrAl2O4 : Eu2+, Dy3+) in Ethyl Vinyl Acetate copolymer (EVA). The modifications of chemical and physical properties of these films were investigated upon irradiation using wavelengths beyond 300 nm. The presence of fillers was revealed to be a pro-degrading factor of the composite films, without existence of any change of the degradation mechanism of the polymer. The propagation of light within these films was carefully investigated by applying Mie theory. The results highlight a possible increase of the light optical path in composite films due to scattering. This phenomenon might contribute to explain the photochemical behavior of the studied films. At last, a proof of concept was searched for the design of multifunctional coatings able to increase and preserve the conversion properties of a P3HT based OSC.

The optical response of several magnetic nanoparticle dispersions is studied by angle resolved transmittance at wavelength of 600 nm in zero-field and under an applied magnetic field of 0.1 T, with the purpose of exploring to what extent this could be used as a method of monitoring the colloidal dispersions. In an external magnetic field, magnetic particles will start to order into needle-like structures aligned with the field, which was observed by microscopy. This will change the light scattering caused by the particles. Results showed a clear effect from applying the magnetic field by a dip in the transmitted intensity at angles around 3-5 degrees. The scattering is compared to that of a homogeneous infinite cylinder and theoretical explanations to the effect are discussed. Spectrophotometry at wavelengths between 300-1100 nm is performed and compared with calculations from Kubelka-Munk approximation to give a first characterization of the particle dispersions. Particles used in this project are magnetite, Fe3O4, and maghemite, gamma-Fe2O3, nanoparticles with sizes ranging from 5-250 nm.

Orientador: Edvaldo Sabadini / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T20:28:41Z (GMT). No. of bitstreams: 1 Clinckspoor_KarlJan_M.pdf: 16885506 bytes, checksum: bf5bdbaa99957493be29510c93bbd89d (MD5) Previous issue date: 2015 / Resumo: O papel estrutural de cossolutos derivados de cinamato para a formação de micelas gigantes de surfactantes catiônicos. Micelas gigantes (MG) são estruturas de autoassociação de surfactantes que podem ser formadas pela adição de cossolutos aromáticos, como salicilato, a soluções de surfactantes catiônicos como CTAB e TTAB (brometo de cetiltrimetilamônio e brometo de tetradeciltrimetilamônio). Estudou-se o papel de derivados estruturais do ácido cinâmico (C6H6-CH=CH-COOH), a saber, ácido ortohidroxicinâmico (OHCA), ácido ortometoxicinâmico (OMCA), ácido ortohidroxifenilpropiônico (OHPA), ácido 3-fenilpropiônico (3PPA) na formação de MG de CTAB e TTAB, em pH 6, e também foi estudada a variação de pH de soluções com OHCA, entre pH 6 e 11. As técnicas principais utilizadas foram: Reologia oscilatória, Espalhamento estático de luz (SLS), Calorimetria de titulação isotérmica (ITC), Espalhamento de raio X em baixo ângulo (SAXS) e Microscopia de transmissão eletrônica em temperaturas criogênicas (Cryo-TEM). Variando a estrutura dos cossolutos, foi possível observar que tanto a presença da ligação dupla do cinamato quanto a de uma hidroxila na posição orto contribuem para a formação de MGs. Quando o cossoluto possui esses dois grupos, que é o caso do OHCA, as micelas são formadas em proporções muito baixas de [TTAB]/[Cossoluto], como foi visto por ITC. Quando o cossoluto possui somente um dos grupos, a formação de micelas ocorre em proporções maiores (OHPA, OMCA, Cinamato) e quando possui nenhum dos dois grupos (3PPA), não são formadas micelas gigantes. As estruturas das micelas de cada região do ITC foram inferidas por SLS e ensaios viscosimétricos. Variando-se o pH das soluções de OHCA com TTAB, observou-se que quanto maior o pH, as micelas são formadas em proporções maiores e a entalpia de formação é menor. Por reologia, foi visto que em pH 9, o sistema formado possui um tempo de relaxação muito maior que em pHs 6-8, em pH 10 o sistema não é mais Maxwelliano e em pH 11, a solução é fluída como água. Isso ocorre porque, quanto maior o pH, o OHCA se torna mais hidrofólico e menor é sua partição no interior da micela / Abstract: The structural role of cossolutes derived from cinnamate in the formation of cationic surfactante wormlike micelles. Wormlike micelles (WLM) are surfactant self-assembly structures that can be formed by the addition of aromatic cossolutes, like salicylate, to solutions of cationic surfactants like CTAB and TTAB (cetyltrimethylammonium bromide and tetradecyltrimethylammonium bromide). We studied the structural role of structural derivatives of cinnamic acid (C6H6-CH=CH-COOH), namely, orthohydroxycinnamic acid (OHCA), orthomethoxycinnamic acid (OMCA), orthohydroxyphenylproprionic acid (OHPA), 3-phenylpropionic acid (3PPA) on the formation of wormlike micelles of CTAB and TTAB, at pH 6. We also studied the variation of pH, ranging from 6 to 11, on OHCA WLM. The main techniques used were: Oscillatory rheology, static light scattering (SLS), isothermal titration calorimetry (ITC), small angle x-ray scattering (SAXS) and cryogenic temperature transmission electron microscopy (Cryo-TEM). By varying the structure of the cossolutes, it was possible to see that both the presence of a double bond and an ortho-hydroxyl favor the formation of WLM. When the cossolute has both groups (OHCA), the WLM are formed at very low [TTAB]/[Cossolute], as was seen by ITC. When the cossolute has only one of those groups the WLMs are formed at higher proportions (OHPA, OMCA, Cinnamate) and when it doesn't have either groups (3PPA), no WLMs are formed. The structures at each concentration region were inferred by viscosimetry and SLS. When varying the pH of OHCA, it was observed that the higher the pH, the proportion for the formation of WLM is increased, and the enthalpy of formation is smaller. By rheology it was seen that at pH 9, the system formed has a much higher relaxation time than at pH 6-8, at pH 10 the system isn't Maxwellian and at pH 11, the system is liquid. This occurs because by increasing the pH, the hydrophilicity of OHCA is increased, and smaller is its partition on the WLM palisade / Mestrado / Físico-Química / Mestre em Química

This thesis deals with the aggregation behaviour of palmitoylhyaluronan in two degrees of substitution, namely 10 % and 16 %. Using a fluorescence spectroscopy method with pyrene as a fluorescence probe, we found a critical micellar concentration. The results were confirmed by measuring the dynamic light scattering, which also showed an increase in the size of aggre-gates with an increasing concentration. System stability is reduced by increased ionic strength as evidenced by zeta potential measurement. Experiments found that 16 % substitution sample can form a gel. The gel is very stiff and has excellent properties, which was confirmed by rhe-ology. We also managed to incorporate pyrene in the gel, which was demonstrated by the presence of highly solvated domains that could be polymer micelles. Based on these results, 16% substitution sample was subjected the MTT assay to cytotoxicity. The results confirmed that the examined sample was not toxic.

A Matlab numerical model for scattering simulation was proposed based on the solution derived from the Beckmann-Kirchhoff scalar theory of scattering of electromagnetic waves from rough surfaces. A series of various synthetic surface samples were obtained using the open source software Gwyddion on which numerical simulations of scattering were carried out. The validity of this numerical model was tested and compared with experimental results.

Zařízení založená na spinových vlnách mají potenciál být využita ve výpočetní technice s nízkou spotřebou energie. Pro úspěšné využití je samozřejmě potřeba spojit více takových zařízení na jednom čipu, součástí čehož musí být zatáčení spinových vln zahnutými vlnovody. Problém zatáčení spinových vln v dipolárně výměnném režimu zatím nebyl uspokojivě vyřešen, vyzkoušené přístupy vedly ke ztrátě intenzity a fázové koherence. V této diplomové práci jsme zkoumali dva systémy, které by mohly být využity k zatáčení spinových vln. Prvním z nich jsou tenké metastabilní vrstvy slitiny železa a niklu. Paramagnetická metastabilní fcc vrstva, která byla epitaxně narostena na substrátu z mědi, může být transformována do stabilní ferromagnetické bcc fáze pomocí fokusovaného iontového svazku. Tato technika nám dává prostorovou kontrolu nad transformačním procesem a strategie skenování svazkem nám dokonce umožňuje určit směr mangetické anisotropie. Magnetické vlastnosti struktur vytvořených touto metodou a lom spinových vln mezi doménami s odlišným směrem magnetické anisotropie byly změřeny pomocí mikroskopie Brillouinova rozptylu světla. Druhým zkoumaným systémem jsou zvlněné vlnovody, jejichž zvlnění indukuje magnetickou anisotropii. Zvlnění magnetické vrstvy je vytvořeno depozicí nemagnetických vlnek na substrátu indukovanou fokusovaným elektronovým svazkem a následnou depozicí magnetického materiálu. Byly vyrobeny různé návrhy zatočených zvlněných vlnovodů a změřili jsme šíření spinových vln jejich zatáčkami pomocí mikroskopie Brillouinova rozptylu světla. Využili jsme také mikromagnetické simulace pro získání hlubšího porozumění zkoumané problematiky a pro hledání vhodných návrhů experimentů.

The aim of this thesis was to prepare hyaluronic acid micro- and nanoparticles based on electrostatic interactions with oppositely charged molecules. Following parameters were monitored: correlation function behavior, the particle size and zeta potential value. At the beginning, it was necessary to study the behavior of hyaluronan in solution by dynamic light scattering measurement. Micro- and nanoparticles were prepared by mixing different volume ratios of negatively charged hyaluronan and positively charged polyarginine or cetyltrimethylammonium bromide. Micro- and nanoparticles were prepared in aqueous solution as well as in 0,15 M sodium chloride solution (physiological solution). In the case of the hyaluronan solution a polydisperse character of hyaluronan was detected. It was found that the dissolution of hyaluronan in the physiological solution gives us the smaller particle size in opposite to particle size obtained from the same concentrations of hyaluronan dissolved in water. Furthermore, it was found that systems composed of hyaluronan and polyarginine create particle size of about 100 nm. Whereas systems consisting of cetyltrimethylaminoum bromide and hyaluronan form larger particles, in units of hundreds of nanometers, the particle size in physiological solution were smaller than the same systems dissolved in aqueous solution.

This thesis is focused on investigation of phospholipid-hyaluronan system. First, appropriate method for preparation of bulk solution of phospholipid/lipid and suitable fluorescence probe were chosen. Sonification was selected as a method for preparation of bulk solution and pyrene was chosen as a fluorescence probe. From the group of phospholipids lecithin was selected. Next to phospholipid, lipid with no phosphate group (DPTAP) was utilized for comparison, alternatively a mixture of lipid (DPTAP) and phospholipid (DPPC). Instead of hyaluronan another polyelectrolytes (sodium polystyrene sulfonate, sodium alginate) were used too. Measurements were performed in water environment and in phosphate buffer saline (PBS). All investigation was accomplished by fluorescence spectroscopy and dynamic light scattering.

The effect of hydrophobically modified hyaluronan on surfactants aggregation has been studied in this master’s thesis. The value of critical micelle concentration of anionic surfactant SDBS (sodium dodecylbenzensulfonate), cationic surfactant CTAB (cetyltrimethylamonnium bromide) and nonionic surfactant Triton X-100 (octylphenol ethoxylate) was determined by fluorescence spectroscopy using pyrene probe. Aggregation behavior of surfactants was performed with addition of hydrophobically modified hyaluronan of two molecular weights (17 kDa, 206 kDa) in aqueous solution. The greatest influence of hydrophobized hyaluronan on aggregation behavior was observed in system with cationic surfactant CTAB. Stability of system containing cationic surfactant and hydrophobically modified hyaluronan was established through zeta potential. Last part of thesis deals with size determination using dynamic light scattering.

This master thesis is focused on the evaluation of the influence of particle surface properties on the results of microrheological measurements with biopolymer solutions. Hyaluronan has been chosen as negatively charged polymer, chitosan as positively charged polymer and glycerol and its solutions of various concentrations were used as homogenous model systems. Dynamic light scattering and single particle tracking microrheology were chosen from passive microrheological techniques. Particles with various surface modifications (neutral, positive surface charge and negative surface charge) were used for the experiments. The results of microrheological techniques were then compared with classic rheology and moreover the glycerol results were compared with tabulated values.