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Orientador: David Mendez Soares / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-17T17:51:55Z (GMT). No. of bitstreams: 1 Gomide_AndrezaBarbosa_D.pdf: 5782130 bytes, checksum: 73ea74eba4132f68eced1394071826de (MD5) Previous issue date: 2011 / Resumo: Frente à complexidade estrutural e funcional das membranas biológicas, a construção de membranas modelo sobre suporte sólido surge como uma resposta para o estudo daquelas. Para acessar as propriedades estruturais e funcionais de uma membrana biológica é fundamental que a membrana modelo seja capaz de refletir a interface membrana/ambiente aquoso. Portanto, foi feito um estudo da água frente à superfície sólida e verificou-se que a água frente a superfícies pode apresentar estrutura e propriedades físicas como densidade, viscosidade, constante dielétrica, etc. diferentes da águas da massa líquida (bulk water). Também investigamos a formação de filmes de fosfolipídios sobre o eletrodo de ouro a partir de soluções de lipossomos. A microbalança de cristal de quartzo (QCM) mostrou os processos de adsorção de lipossomos à superfície do eletrodo de ouro, de ruptura e formação de filmes. Usando a técnica de filmes de Langmuir, determinamos a densidade de fosfolipídios em uma membrana modelo e comparamos com os resultados gravimétricos obtidos com a QCM. Com a técnica de miscroscopia de força atômica (AFM) usando medidas de força vs. distância, detectamos a espessura do filme de DMPC (6 nm). Além disso, mostramos que na presença de uma solução 0,5 M de H2SO4 o filme formado apresenta uma rugosidade na superfície que muda conforme o potencial aplicado ao eletrodo / Abstract: Faced with structural and functional complexity of biological membranes, the construction of model membranes on solid support appears as a response to the study of those. To access the structural and functional properties of a biological membrane, it is crucial that the membrane model is able to reflect the interface membrane/aqueous environment. Therefore, a study was made of water contacting a solid surface. It was found that water close to surfaces can have structure and physical properties (as density, viscosity, dielectric constant, etc..) different from bulk water. We also investigated the formation of phospholipid films on the gold electrode from solutions of liposomes. The quartz crystal microbalance (QCM) showed the adsorption of liposomes to the surface of gold electrode, breakdown and formation of a film. Using the technique of Langmuir we determined the density of phospholipids in a membrane model and compared with the gravimetric results obtained with the QCM. With the atomic force microscope (AFM) using the force vs. distance measurement we detected a 6 nm thick DMPC film on the electrode. Furthermore, we showed that in the presence of a 0.5 M solution of H2SO4 the film formed on the surface has a roughness that changes with the applied potential to the electrode / Doutorado / Físico-Química / Doutora em Ciências

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This thesis presents the development and redesign of a commercial electrochemical quartz crystal microbalance with dissipation (E–QCM–D). This was used to study factors affecting the efficiency of the four electron reduction catalysed by the fuel cell enzyme bilirubin oxidase from Myrothecium verrucaria immobilised on thiol modified gold surfaces. Within this thesis, the E–QCM–D was used to show that application of a constant potential to bilirubin oxidase adsorbed to thiol-modified gold surfaces causes activity loss that can be attributed to a change in structural arrangement. Varying the load by potential cycling distorts the enzyme by inducing rapid mass loss and denaturation. Attaching the enzyme covalently reduces the mass loss caused by potential cycling but does not mitigate activity loss. Covalent attachment also changes the orientation of the surface bound enzyme as verified by the position of the catalytic wave (related to the overpotential for catalysis) and reactive labelling followed by mass spectrometry analysis. The E–QCM–D was used to show how electrostatic interactions affect enzyme conformation where high pH causes a reduction in both mass loading at the electrode and a reduction in activity. At pH lower than the enzyme isoelectric point, there is a build up of multilayers in a clustered adsorption. When enzyme adsorbs to hydrophobic surfaces there is a rapid denaturation which completely inactivates the enzyme. Changing the surface chemistry from carboxyl groups to hydroxyl and acetamido groups shows that catalysis is shifted to more negative potentials as a result of an enzyme misorientation. Further to this, increasing the chain length of the thiol modifier indicates that an increased distance between surface and enzyme reduces activity, enzyme loading and results in a conformational rearrangement that permits electron transfer over longer distances.