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Magnetic nanoparticles coated with polymers hold great promise as materials for applications in biotechnology. In this body of work, magnetic fluids for the treatment of retinal detachment are examined closely in three regimes; motion of ferrofluid droplets in aqueous media, size analysis of the polymer-iron oxide nanoparticles, and calculation of interparticle potentials as a means for predicting fluid stability. The macromolecular ferrofluids investigated herein are comprised of magnetite nanoparticles coated with tricarboxylate-functional polydimethylsiloxane (PDMS) oligomers. The nanoparticles were formed by reacting stoichiometric concentrations of iron chloride salts with base. After the magnetite particles were prepared, the functional PDMS oligomers were adsorbed onto the nanoparticle surfaces. The motion of ferrofluid droplets in aqueous media was studied using both theoretical modeling and experimental verification. Droplets (~1-2 mm in diameter) of ferrofluid were moved through a viscous aqueous medium by an external magnet of measured field and field gradient. Theoretical calculations were made to approximate the forces on the droplet. Using the force calculations, the times required for the droplet to travel across particular distances were estimated. These estimated times were within close approximation of experimental values. Characterization of the sizes of the nanoparticles was particularly important, since the size of the magnetite core affects the magnetic properties of the system, as well as the long-term stability of the nanoparticles against flocculation. Transmission electron microscopy (TEM) was used to measure the sizes and size distributions of the magnetite cores. Image analyses were conducted on the TEM micrographs to measure the sizes of approximately 6000 particles per sample. Distributions of the diameters of the magnetite cores were determined from this data. A method for calculating the total particle size, including the magnetite core and the adsorbed polymer, in organic dispersions was established. These estimated values were compared to measurements of the entire complex utilizing dynamic light scattering (DLS). Better agreement was found for narrow particle size distributions as opposed to broader distributions. The stability against flocculation of the complexes over time in organic media were examined via modified Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations. DLVO theory allows for predicting the total particle-particle interaction potentials, which include steric and electrostatic repulsions as well as van der Waals and magnetic attractions. The interparticle potentials can be determined as a function of separation of the particle surfaces. At a constant molecular weight of the polymer dispersion stabilizer, these calculations indicated that dispersions of smaller PDMS-magnetite particles should be more stable than those containing larger particles. The rheological characteristics of neat magnetite-PDMS complexes (i.e, no solvent or carrier fluid were present) were measured over time in the absence of an applied magnetic field to probe the expected properties upon storage. The viscosity of a neat ferrofluid increased over the course of a month, indicating that some aggregation occurred. However, this effect could be removed by shearing the fluids at a high rate. This suggests that the particles do not irreversibly flocculate under these conditions. / Ph. D.

Ionic Liquids (ILs) has been attracting attention, both from academia and industry, given the numerous applications of these systems. ILs are salts, usually composed by an organic ion, and a counterion which could be organic or inorganic, and, interestingly they are found at liquid state at room temperature. Our interest in studying ILs comes from its low toxicity. Some recent studies have shown that the toxicity of the ILs ishigher than believed, in particular for biologically relevant systems. The main goal of this research is to study the influence of the ionic liquid 1-tetradecyl-3-methylimidazolium chloride ([C14MIM][Cl]) with membrane systems. To do so, we made use of different lipids: POPC, Sphingomyelin, Cholesterol, POPG, DPPC, DPPG and DMPC. For each of these systems, the influence of ILs concentration were elucidated by means of a systematic study through different experimental techniques: Small Angle X-ray scattering (SAXS), dynamic light scattering (DLS), fluorescence anisotropy, optical microscopy and z-potential. Since [C14MIM][Cl] has a positive charge on the imidazolium group, the superficial charge of all vesicles increased. For zwitterionic vesicles no significant change in size and melting temperature were noticed. The imidazolium-based ionic liquid diminished the gel-fluid transition temperature for negatively charged lipids. For DPPC:DPPG (1:1), for instance, the transition temperature decreased from 42.50±0.13oC to 25.27±0.33oC and for DPPG from 46.12±0.22 oC to 36.6±0.38 oC. For DPPG, the vesicle hydrodynamic diameter increased from 84±0.1nm to 176±0.1nm, whereas for DPPC:DPPG it increased from 95±0.1nm to 196±0.1nm. The electronic density profile, obtained by SAXS, supported the penetration of the [C14MIM][Cl] into the negative bilayer structure. 15 mol% of [C14MIM][Cl] increased the polar head thickness of DPPC vesicles from 11.1±0.6 Å to 18.0±0.7 Å, without alter significantly the inner region of the membrane.Qualitative results obtained with optical microscopy showed that the IL incorporation destabilize the membrane asymmetry (between the leaflets) leading to the formation of pores (evidenced by optical contrast lost) and the presence of buds. We believe that this work could improve the understanding of the effects of ILs in the presence of biological relevant systems / Os líquidos iônicos (LI) tem atraído grande atenção, tanto da academia quanto da indústria, devido às suas numerosas aplicações. LI são sais, normalmente compostos por um íon orgânico, e um contra-íon que pode ser orgânico ou inorgânico, mas que tem como característica ser encontrado no estado líquido à temperaturas próximas a ambiente. Nosso interesse em estudar LIs vem de sua baixa toxicidade, atribuída a sua baixa volatilidade. Entretanto, alguns estudos recentes mostraram que a toxicidade dos LI é maior do que se acreditava, em particular com sistemas de relevância biológica.O objetivo principal desta dissertação é estudar a influência do líquido iônico 1-tetradecil-3-metilimidazólio cloreto ([C14MIM][Cl]) com sistemas de membrana. Para isso, utilizamos diferentes lipídios, como o POPC, esfingomielina, colesterol, POPG, DPPC,DPPG e o DMPC. Para cada um destes sistemas, a influência da concentração de LI foi elucidada por meio de um estudo sistemático através de diferentes técnicas experimentais, tais como: espalhamento de raio-X a baixos ângulos (SAXS), espalhamento dinâmico de luz (DLS), anisotropia de fluorescência, microscopia óptica e potencial-z. Uma vez que o componente iônico de [C14MIM][Cl] tem uma carga positiva no grupo imidazólio, a carga superficial de todas as vesículas estudadas aqui aumentou. Entretanto, para asvesículas compostas pelos lipídeos zwitteriónicos, não tenha sido observada qualquer alteração significativa no tamanho e na temperatura de transição de fase gel-fluido. O [C14MIM][Cl] altera a organização interna entre as moléculas de lipídio com carga negativa. Consequentemente, à medida que a quantidade de LI aumenta, a temperatura de transição de fase diminui e o tamanho médio das vesículas aumenta. Para o sistema DPPC:DPPG (1:1) a temperatura de transição de fase caiu de 42.50 ± 0.13 oC para 25.27 ± 0.33 oC e para as vesículas de DPPG de 46.12±0.22 oC para 36.6±0.38 oC. Quanto ao diâmetro hidrodinâmico médio, no caso do DPPG este valor aumentou de 84±0.1 nm para 176±0.1 nm, enquanto que para a mistura DPPC:DPPG (1:1) ele passou de 95±0.1nm para 196±0.1nm. Indicando assim que o LI incorpora na bicamada lipídica negativamente carregada. O perfil de densidade eletrônica, obtido por SAXS, confirma a penetração do [C14MIM][Cl] na bicamada lipídica. Diferentemente, para a membrana lipídica zwitteriónica o LI tende a se situar perto da região da cabeça polar sem afetar significativamente a região do interior da bicamada lipídica. Por outro lado, a presença de15 mol% de [C14MIM][Cl] aumenta a espessura da região polar das bicamadas das vesículas de DPPC de ~ 11.1±0.6 Å para ~ 18.0±0.7 Å. Os resultados qualitativos da microscopia óptica mostraram que a incorporação da LI desestabiliza a assimetria da membrana entre as camadas interna e externa, além de sugerir o aparecimento de poros (evidenciado pela perda do contraste ótico das vesículas) e estruturas chamadas de buds. Esperamos que este trabalho melhore a compreensão dos efeitos do LI na presença de organismos biológicos.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2018-06-05T14:40:04Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Schardosin, Janaina.pdf: 3840457 bytes, checksum: ffe3148238384650d2997e09aff27ed0 (MD5) / Made available in DSpace on 2018-06-05T14:40:04Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Schardosin, Janaina.pdf: 3840457 bytes, checksum: ffe3148238384650d2997e09aff27ed0 (MD5) Previous issue date: 2018-04-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O processo de humificação, conversão de resíduos orgânicos em húmus, é um fator importante na compreensão da dinâmica da matéria orgânica. A sua quantificação, é fundamental para o estudo da evolução química dessa substância. O objetivo deste trabalho foi caracterizar as amostras de ácidos húmicos (AHs) e quantificar o grau de humificação do solo e das frações físicas (por tamanho de partículas). As análises de Espectroscopias de Fluorescência de Raios X por Dispersão de Comprimento de Onda, Fluorescência na região do Visível, Espectroscopia Vibracional na região de Infravermelho e de Absorção na região do Ultravioleta e Vísivel, Espectrocospia Raman, acompanhadas das técnicas de Análise Térmica, Microscopia Eletrônica de Varredura com Canhão Eletrônico por Efeito de Campo e Espalhamento Dinâmico da Luz foram utilizadas. A quantificação do grau de humificação mostrou que AHs extraídos da profundidade (10- 20 cm) possuem estruturas aromáticas mais condensadas. A fração de AH que apresentou maior grau de humificação foi a extraída do solo com a adição de calagem, o que demonstra uma influência do calcário na aceleração do processo de humificação. O estudo das frações granulométricas do solo, determinou, com espectroscopia de infravermelho, os atributos orgânicos que estão associados as frações do solo e, que a maioria dos minerais presentes nas frações granulométricas, foram identificados como sendo caulinita, haloisita, quartzo e gibbsita. Já para o estudo da humificação dos AHs extraídos das frações granulométricas, a quantificação do grau de humificação, do maior para o menor, é procedente da fração silte, seguidos da fração argila e, por fim, a fração areia. / The humification process, conversion of organic waste into humus, is an important factor to understand the organic matter dynamics. Its quantification is vital for the study of this substance chemical evolution. This study aimed at characterizing humic acid (HA) samples and quantify the degree of soil humification and physical fractions (particle size). The analysis of Spectroscopies of wavelenght dispersive X-ray fluorescence, visible fluorescence, vibrational infrared region, ultraviolet and visible light absorption and Raman along with the techniques of Thermal Analysis, scanning electron microscopy with field effect gun and dynamic light scattering were employed. The humification degree quantification revealed that the HA extracted from the 10-20cm depth presented more polycondensed structures. The HA fraction that presented the highest humification degree was extracted from the soil with the addition of liming, which demonstrates the limestone influence in the acceleration of the humification process. The study of the soil granulometric fractions determined, with infrared spectroscopy, the organic properties that are associated to soil fractions and that most of the minerals present in the granulometric fractions, were identified as kaolinite, halloysite, quartz and gibbsite.The study of the humification in the HA extracted from the granulometric fractions quantified the humification degree and revealed the highest values in the silt fraction followed by the clay fraction and, finally, the lowest values were found in the sand fraction.

Ionic Liquids (ILs) has been attracting attention, both from academia and industry, given the numerous applications of these systems. ILs are salts, usually composed by an organic ion, and a counterion which could be organic or inorganic, and, interestingly they are found at liquid state at room temperature. Our interest in studying ILs comes from its low toxicity. Some recent studies have shown that the toxicity of the ILs ishigher than believed, in particular for biologically relevant systems. The main goal of this research is to study the influence of the ionic liquid 1-tetradecyl-3-methylimidazolium chloride ([C14MIM][Cl]) with membrane systems. To do so, we made use of different lipids: POPC, Sphingomyelin, Cholesterol, POPG, DPPC, DPPG and DMPC. For each of these systems, the influence of ILs concentration were elucidated by means of a systematic study through different experimental techniques: Small Angle X-ray scattering (SAXS), dynamic light scattering (DLS), fluorescence anisotropy, optical microscopy and z-potential. Since [C14MIM][Cl] has a positive charge on the imidazolium group, the superficial charge of all vesicles increased. For zwitterionic vesicles no significant change in size and melting temperature were noticed. The imidazolium-based ionic liquid diminished the gel-fluid transition temperature for negatively charged lipids. For DPPC:DPPG (1:1), for instance, the transition temperature decreased from 42.50±0.13oC to 25.27±0.33oC and for DPPG from 46.12±0.22 oC to 36.6±0.38 oC. For DPPG, the vesicle hydrodynamic diameter increased from 84±0.1nm to 176±0.1nm, whereas for DPPC:DPPG it increased from 95±0.1nm to 196±0.1nm. The electronic density profile, obtained by SAXS, supported the penetration of the [C14MIM][Cl] into the negative bilayer structure. 15 mol% of [C14MIM][Cl] increased the polar head thickness of DPPC vesicles from 11.1±0.6 Å to 18.0±0.7 Å, without alter significantly the inner region of the membrane.Qualitative results obtained with optical microscopy showed that the IL incorporation destabilize the membrane asymmetry (between the leaflets) leading to the formation of pores (evidenced by optical contrast lost) and the presence of buds. We believe that this work could improve the understanding of the effects of ILs in the presence of biological relevant systems / Os líquidos iônicos (LI) tem atraído grande atenção, tanto da academia quanto da indústria, devido às suas numerosas aplicações. LI são sais, normalmente compostos por um íon orgânico, e um contra-íon que pode ser orgânico ou inorgânico, mas que tem como característica ser encontrado no estado líquido à temperaturas próximas a ambiente. Nosso interesse em estudar LIs vem de sua baixa toxicidade, atribuída a sua baixa volatilidade. Entretanto, alguns estudos recentes mostraram que a toxicidade dos LI é maior do que se acreditava, em particular com sistemas de relevância biológica.O objetivo principal desta dissertação é estudar a influência do líquido iônico 1-tetradecil-3-metilimidazólio cloreto ([C14MIM][Cl]) com sistemas de membrana. Para isso, utilizamos diferentes lipídios, como o POPC, esfingomielina, colesterol, POPG, DPPC,DPPG e o DMPC. Para cada um destes sistemas, a influência da concentração de LI foi elucidada por meio de um estudo sistemático através de diferentes técnicas experimentais, tais como: espalhamento de raio-X a baixos ângulos (SAXS), espalhamento dinâmico de luz (DLS), anisotropia de fluorescência, microscopia óptica e potencial-z. Uma vez que o componente iônico de [C14MIM][Cl] tem uma carga positiva no grupo imidazólio, a carga superficial de todas as vesículas estudadas aqui aumentou. Entretanto, para asvesículas compostas pelos lipídeos zwitteriónicos, não tenha sido observada qualquer alteração significativa no tamanho e na temperatura de transição de fase gel-fluido. O [C14MIM][Cl] altera a organização interna entre as moléculas de lipídio com carga negativa. Consequentemente, à medida que a quantidade de LI aumenta, a temperatura de transição de fase diminui e o tamanho médio das vesículas aumenta. Para o sistema DPPC:DPPG (1:1) a temperatura de transição de fase caiu de 42.50 ± 0.13 oC para 25.27 ± 0.33 oC e para as vesículas de DPPG de 46.12±0.22 oC para 36.6±0.38 oC. Quanto ao diâmetro hidrodinâmico médio, no caso do DPPG este valor aumentou de 84±0.1 nm para 176±0.1 nm, enquanto que para a mistura DPPC:DPPG (1:1) ele passou de 95±0.1nm para 196±0.1nm. Indicando assim que o LI incorpora na bicamada lipídica negativamente carregada. O perfil de densidade eletrônica, obtido por SAXS, confirma a penetração do [C14MIM][Cl] na bicamada lipídica. Diferentemente, para a membrana lipídica zwitteriónica o LI tende a se situar perto da região da cabeça polar sem afetar significativamente a região do interior da bicamada lipídica. Por outro lado, a presença de15 mol% de [C14MIM][Cl] aumenta a espessura da região polar das bicamadas das vesículas de DPPC de ~ 11.1±0.6 Å para ~ 18.0±0.7 Å. Os resultados qualitativos da microscopia óptica mostraram que a incorporação da LI desestabiliza a assimetria da membrana entre as camadas interna e externa, além de sugerir o aparecimento de poros (evidenciado pela perda do contraste ótico das vesículas) e estruturas chamadas de buds. Esperamos que este trabalho melhore a compreensão dos efeitos do LI na presença de organismos biológicos.

Une étude haut-débit de la polycondensation du silicate est réalisée grâce à des outils robotisés couplés à des mesures macroscopiques (turbidité, gélification). Cette approche permet de dégager les limites de gélification d'un silicate industriel ainsi que les mécanismes mis en jeu. Cette thèse présente aussi deux outils miniaturisés basés sur des technologies microfluidiques, adaptés à des mesures in-situ et sous écoulement de diffusion des rayons X aux petits angles et de diffusion dynamique de la lumière. Ces outils permettent d'étudier les mécanismes de la polycondensation du silicate de sodium dans le procédé industriel, à des échelles de temps courtes (1 à 10 s). / Abstract

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-02-13T19:11:35Z No. of bitstreams: 1 MarianaAlvesLeiteDutra_DISSERT.pdf: 2825637 bytes, checksum: 18b7c74e24edf8e546ebd99e18dff673 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-02-14T00:26:44Z (GMT) No. of bitstreams: 1 MarianaAlvesLeiteDutra_DISSERT.pdf: 2825637 bytes, checksum: 18b7c74e24edf8e546ebd99e18dff673 (MD5) / Made available in DSpace on 2017-02-14T00:26:45Z (GMT). No. of bitstreams: 1 MarianaAlvesLeiteDutra_DISSERT.pdf: 2825637 bytes, checksum: 18b7c74e24edf8e546ebd99e18dff673 (MD5) Previous issue date: 2016-07-18 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / A s?ntese de pol?meros usando solventes org?nicos e nocivos ao meio ambiente tem sido frequente na comunidade cient?fica. O uso de solventes verdes, como a ?gua, agride menos o meio ambiente. Este estudo proporcionou a s?ntese de dois copol?meros de poli(N-isopropilacrilamida-co-laurato de vinila) com diferentes percentuais molares dos mon?meros na cadeia polim?rica e a avalia??o de suas propriedades. A polimeriza??o foi realizada via radicais livres, substituindo o solvente org?nico, THF, pela ?gua e o iniciador, AIBN, por persulfato de pot?ssio (K2S2O8). Para fins de avalia??o da contribui??o do laurato de vinila nos copol?meros, tamb?m foi sintetizado o homopol?mero de NIPAAm, nas mesmas condi??es reacionais empregadas para os copol?meros. As estruturas qu?micas dos pol?meros obtidos foram investigadas por espectroscopia no infravermelho (IV) e resson?ncia magn?tica nuclear de hidrog?nio (1H RMN) e de carbono (13C RMN). Solu??es aquosas dos pol?meros foram analisadas por reometria, espalhamento de luz est?tico (SLS) e din?mico (DLS). Os resultados obtidos por reometria mostraram que a temperatura cr?tica consoluta inferior (LCST) do poli(N-isopropilacrilamida-co-laurato de vinila) contendo 7 mol% de LV foi de 26 ?C, enquanto a do copol?mero contendo 13 mol% de LV foi de 21 ?C, ou seja, mais baixas que a LCST da PNIPAAm (34 ?C). Esse resultado indica que a presen?a do mon?mero hidrof?bico, LV, contribuiu significativamente para a diminui??o da LCST do pol?mero. A partir do espalhamento de luz est?tico (SLS), calculou-se a massa molar ponderal m?dia aparente ( ?w), o raio de giro (Rg) e o segundo coeficiente virial (A2) dos pol?meros. A ?w e o A2 do poli(N-isopropilacrilamida-co-laurato de vinila) contendo 7 mol% de LV foi de 3,0x106 g/mol e 16,1 mol.L.g-2, respectivamente, enquanto que para o copol?mero contendo 13 mol% de LV, os valores obtidos para ?w e o A2 foram de 2,6x106 g/mol e - 4,27 mol.L.g-2, respectivamente. Para a PNIPAAm, os valores obtidos de ?w e A2 foram 3,2x107 g/mol e 0,69 mol.L.g-2, respectivamente. A diminui??o do valor de ?w dos copol?meros em rela??o ao valor da ?w da PNIPAAm foi atribu?da ? redu??o das intera??es pol?mero-solvente no meio, que foi confirmada pela diminui??o do valor do A2 para os copol?meros. As an?lises de DLS, feitas em concentra??o 1g/L no intervalo de temperatura 15 ?C a 40 ?C, indicaram a presen?a de cadeias isoladas e agregados de diversos tamanhos para os pol?meros em solu??o. / The synthesis of polymers using organic solvents harmful to the environment has been frequent in the scientific community. The use of green solvents, such as water, causes less damage to the environment. This study provided the synthesis of two copolymers of poly (N-isopropylacrylamide-co-vinyl laurate), with different molar percentage of monomers in the polymer chain and the evaluation of their properties. The polymerizations were carried out by free radicals, replacing the organic solvent THF by water, and AIBN initiator by potassium persulfate (K2S2O8). In attempt of evaluating the contribution of vinyl laurate (VL) in copolymers, the NIPAAm homopolymer was also synthesized under the same reaction conditions employed for the copolymers. The chemical structures of the synthesized polymers were determined through infrared (IR) and nuclear magnetic resonance spectroscopy. Aqueous solutions of the polymers were analyzed by rheometry, static light scattering (SLS) and dynamic light scattering (DLS). The results of rheometry showed that lower critical solution temperature (LCST) for poly (N-isopropylacrylamide-co- vinyl laurate) containing 7 mol% of VL was 26 ? C, while the copolymer containing 13 mol% VL was 21 ? C. In other words, lower than the LCST of PNIPAAm (34 ? C). There results indicate that the presence of hydrophobic monomer, VL, contributes significantly in reducing the LCST of the polymer. From the static light scattering (SLS) analysis, it was calculated the weight apparent average molecular weight ( ?w), the radius of gyration (Rg) and the second virial coefficient (A2) of the polymers. The ?w and A2 for poly (N-isopropylacrylamide-co-vinyl laurate) containing 7 mol% of VL were 3.0x106 g/mol and 16.1 mol.L.g-2, respectively, while that for the copolymer containing 13 mol% of VL, the values for ?w and A2 were 2.6x106 g/mol and 4.27 mol.L.g-2, respectively. For PNIPAAm, the values of ?w and A2 were 3.2x107 g/mol and 0.69 mol.L.g-2, respectively. The decrease in the value of ?w of the copolymers relative to the ?w value of PNIPAAm was attributed to the reduction of the polymer-solvent interactions in the medium, which was confirmed by decreasing the value of A2 to the copolymers. Dynamic light scattering (DLS) analysis was performance at polymers concentration of 1g/L in the temperature range 15 ?C to 40 ?C and indicated the presence of isolated chains and aggregates of different sizes for the polymers in solution.

L’utilisation de nanoparticules (NPs) dans un milieu biologique est de plus en plus importante, alors que leur assimilation et leur toxicité reste peu maitrisée. Dans ce contexte l’objectif de ce travail est d’étudier l’interaction entre nanoparticules de dioxyde de titane (TiO2) avec des protéines ainsi que leur possible impact sur leurs propriétés structurales. Trois protéines d’intérêt ont été choisies: une protéine de la matrice extra cellulaire, le collagène, et deux protéines du plasma sanguin, l’albumine et le fibrinogène. Le choix a été basé sur l’importance biologique de ces protéines lors des interactions avec des NPs et sur la différence de leurs structures tridimensionnelles. L’étude de l’interaction protéine-NPs a été réalisée en solution et en phase adsorbée dans différentes conditions de température et de temps d’incubation. Dans un premier temps des nanoparticules de dioxyde de titane ont été synthétisées par voie solvothermale, afin d’obtenir des nanoparticules de tailles et de formes contrôlées. Deux types de nanoparticules ont été sélectionnés en vues d’étudier l’effet de forme et de taille sur l’interaction protéines-nanoparticules: des nano-sphères de diamètre de 8 à 10 nm et des nano-bâtonnets d’environ 8 nm de largeur et 23 nm longueur. Leur comportement en solution physiologique ainsi que leur réactivité ont été caractérisé par DSL et absorption UV montrant une inhibition des propriétés catalytiques ainsi qu’une forte agrégation en solution tampon phosphate saline (PBS). Dans un deuxième temps les propriétés d’adsorption du collagène en présence de nanoparticules furent étudiées sur deux types de surfaces l’une hydrophobe et l’autre hydrophile par XPS et imagerie AFM ainsi que par des mesures de forces AFM. Le comportement du collagène en solution en présence de nanoparticules a été caractérisé par ATR liquide. Les observations suggèrent que la formation des fibrilles à l’interface surface-solution de collagène est affectée par le caractère hydrophobe ou hydrophile de la surface ainsi que par la présence de nanoparticules. Enfin les propriétés d’adsorption de la HSA et du fibrinogène en présence de nanoparticules furent étudiées sur une surface hydrophile par imagerie AFM et analyses XPS. Leur comportement en solution en présence de nanoparticules fut étudié par ATR liquide. Les résultats suggèrent deux comportements différents des protéines en présence de nanoparticules pouvant être attribués propriétés physicochimiques différentes des protéines. La HSA subit d’importants changements structuraux en présence de nanoparticules contrairement au fibrinogène.L’étude en phase liquide de l’interaction protéine-nanoparticules couplé à l’étude en phase adsorbées des protéines permet de déterminer les phénomènes impliqués lors de cette interaction ainsi que leurs conséquences sur les protéines, de plus l’utilisation de nanoparticules de taille et forme différentes permet d’étudier la sensibilité des protéines à ces facteurs. / The extensive use of NPs in a biological environment raises the problem of their assimilation or their toxicity, the main objective of this work is to study the interaction of TiO2 NPs with proteins as well as their possible impact on the structural properties of proteins. Three proteins were chosen, a protein of the extracellular matrix, the collagen, and two proteins of the plasma blood, the albumin and the fibrinogen for their biological importance as well as for their various tridimensional structures. The study of the protein-nanoparticle interaction was realized in solution and in the adsorbed phase under various condition of temperature and incubation time. First, titanium dioxide NPs were synthesized by a solvothermal method, NPs with controlled size and form were obtained. Two types of NPs were selected in order to study the effect of shape and size on the protein-NPs interaction: nano-spheres with a diameter of 8 to 10 nm and nano-rods with a width about 8 nm and a length of 23 nm. The behavior in physiological solution as well as the reactivity were characterized by DSL and UV absorption showing an inhibition of catalytic properties as well as a strong aggregation in phosphate buffer saline solution (PBS). Second, the adsorption properties of the collagen in the presence of NPs were studied on two kinds of surfaces, one hydrophobic and the other hydrophilic by XPS and AFM imaging as well as by AFM force measurements. The behavior of the collagen in solution in the presence of NPs was characterized by liquid ATR. The observations suggest that the formation of fibrils at the surface- collagen solution interface is affected by the hydrophobic or the hydrophilic character of the surface as well as by the presence of NPs. In the last part the adsorption properties of HSA and fibrinogen in the presence of NPs were studied on a hydrophilic surface by AFM imaging and XPS analyses. Their behaviors in solution in the presence of NPs were studied by liquid ATR. The results suggest two different behaviors of proteins in the presence of NPs, which can be attributed to the different physico-chemical properties of the proteins. HSA undergoes important structural changes in the presence of NPs but not fibrinogen. The study in the liquid phase of the protein-nanoparticle interaction, coupled to study of proteins in the adsorbed phase allows determining the involved phenomenon during the protein-nanoparticle interaction as well as the consequences on protein adsorption. Moreover, the use of NPs with different sizes and shapes revealed the sensitivity of proteins to these factors.

High surface area of used nanoparticles and their comparable size with polymer chains, are the most important characteristics of fillers in the preparation of non-Newtonian suspensions. Such structures at different concentrations have major influence on the rheological behavior of polymer solution in solvent. With increasing volume fraction of nanofiller, there is pseudoplastic or dilatant behavior present in the dissolved elastomers. Diploma thesis studies the influence of the concentration of different elastomers (SBR and SEBS copolymers) and nanofiller (hydrophobic nanosilica) in suspension, of rheological properties.

Syftet med arbetet var att försöka utveckla en metod för att isolera lipoprotein(a), ett lipoprotein som korrelerar i hög grad till kardiovaskulär sjukdom, från plasma. Det har varit problematiskt att på ett enkelt sätt separera lipoprotein(a) från LDL på grund av dess strukturella likheter. Som inspiration användes en artikel där separationen utfördes med anjonbyteskromatografi-HPLC (high performance liquid chromatography). Målet var att applicera metoden på ett FPLC-system (fast protein liquid chromatography) med en gelfiltreringskolonn och en anjonbyteskolonn där det kaotropiska saltet natriumperklorat användes som elueringsmedel under anjonbyteskromatografin. Resultaten kontrollerades med DLS (dynamic light scattering), SDS-PAGE och Western blot med antikroppar riktade mot lipoprotein(a). Resultaten visade på goda möjligheter till en bra separation vid fortsatta studier.