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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Estudo de filmes de Langmuir e Langmuir-Blodgett de aminas anfifílicas utilizando a espectroscopia SFG / The interaction of water with Langmuir films of amphiphilic amines as a function of pH probed by Pi-A isotherms and SFG spectroscopy

Uehara, Thiers Massami 24 February 2010 (has links)
O estudo da interação de moléculas orgânicas com a água é de grande importância para diversas áreas das ciências, como por exemplo, na compreensão de sistemas biológicos. Uma elevada diversidade de estudos nesta área já foram realizados, no entanto, alguns aspectos do estudo de filmes finos de aminas anfifílicas não foram satisfatoriamente esclarecidos. Este trabalho aborda filmes de Langmuir de octadecilamina em função do pH e da força iônica de subfases aquosas, investigando a estrutura da monocamada orgânica e sua interação com a água, em diversos graus de ionização. Foi utilizada a Espectroscopia Vibracional por Geração de Soma de Frequências (Sum Frequency Generation - SFG), uma técnica que utiliza o princípio da óptica não-linear para estudar superfícies e interfaces, com o objetivo de investigar a conformação molecular dos filmes de Langmuir de aminas anfifílicas de cadeias longas, seu grau de ionização e a estrutura da água interagindo com a monocamada orgânica. Pôde-se acompanhar a ionização da monocamada em função do pH da subfase pela intensidade do modo de estiramento do grupo NH3+, e verificou-se que ela depende do pH local da interface, que por sua vez é alterado pela ionização da monocamada e é sensível à força iônica da subfase. A água interage com a monocamada via ligações de H com os grupos NH2/NH3+ e forma uma camada com alto grau de orientação perpendicular à superfície, mas relativamente desordenada do ponto de vista da rede de ligações de H (como na água líquida). A conformação das cadeias alquila depende da ionização do filme de Langmuir, sendo bastante compacta e ordenada a altos pHs (filme neutro) e mais expandida e desordenada a baixos pHs. Além disso, foram fabricados filmes de Langmuir-Blodgett (LB) de octadecilamina para comparar a estrutura dos filmes na superfície da água e em substratos sólidos. / The study of the interaction of organic molecules with water is of great importance for many areas of science, such as the understanding of biological systems. A large diversity of studies in this area have been performed, however some aspects of the study of thin films of amphiphilic amines have not been satisfactorily clarified. This dissertation focuses on Langmuir films of Octadecylamine as a function of pH and ionic strength of the aqueous subphase, investigating the structure of the organic monolayer and its interaction with water at various degrees of ionization. Sum-Frequency Vibrational Spectroscopy (SFG spectroscopy), a non-linear optical technique to study surfaces and interfaces, was used in order to investigate the molecular conformation of the Langmuir films, its degree of ionization and the structure of water interacting with the organic monolayer. The monolayer ionization could be monitored by the intensity of the NH3+ group stretch mode, and it was found that it depends on the local pH at the interface, which in turn is changed by the monolayer ionization and is sensitive to the subphase ionic strength. Water interacts with the monolayer by H bonds with NH2/NH3+ groups, forming a layer with a high degree of orientational order along the surface normal, but relatively disordered regarding the H-bonding network (like in the bulk liquid). The conformation of the alkyl chains depends on the monolayer ionization, being compact and all-trans at high pHs, but more expanded and disordered at low pHs. In addition, Langmuir-Blodgett (LB) films of Octadecylamine were fabricated to compare their structure on the solid substrate to those on the water surface
32

Thermosensitive gold nanoparticles : solution optical properties and interfacial behaviour / Nanoparticules d’or thermosensibles : propriétés optiques en solution et comportement à l’interface

Said-Mohamed, Cynthia 14 November 2011 (has links)
L’objectif de cette thèse est de contrôler les propriétés optiques des nanoparticules d’or greffées de polymère en modulant les propriétés structurales de la couche protectrice de polymères. Des nanoparticules greffées de polymères thermosensibles avec une large gamme de masse molaire et différents degrés d’hydrophobicité sont synthétisées par la méthode de « grafting-to ». La DNPA est utilisée pour caractériser les propriétés structurales de la couche protectrice de polymère. Les spectres d’absorption sont modélisés en utilisant la théorie de Mie. Nous démontrons que la sensibilité de la SPR à la propriété diélectrique du solvant diminue progressivement avec la fraction volumique de la couche de polymère jusqu’à devenir quasi-nulle; dans ce dernier cas de figure, la SPR est dite « gelée » par la couche de polymère. Un déplacement significatif de la bande de SPR vers le rouge est induit (un changement de couleur se produit) dû à une transition de collapse de la couche de polymère avec la température. La gamme de température pour induire ce déplacement dépend du degré d’hydrophobicité du polymère et de la salinité. Une partie important de cette thèse est également consacrée aux propriétés des nanoparticules d’or greffées de polymères à l’interface air-eau. La technique de Langmuir est utilisée pour former des films minces dont la distance entre particule est contrôlée par la compression, la longueur des chaînes du polymère greffé et la température. Les propriétés structurales des films minces sont étudiées en déterminant la conformation de la couche de polymère greffée et l’organisation du cœur de l’or par la réflectivité de neutron et de X, respectivement. Les mesures de réflectivité nous permettent également d’évaluer et d’améliorer la stabilité des films minces pour un meilleur control de la distance entre particule, aspect important pour l’optimisation de la SPR. Enfin, les propriétés optiques des nanoparticules d’or à l’interface sont mesurées par des mesures de transmission. / In this thesis, the objective is to control the polymer-grafted gold nanoparticles optical properties (SPR) by tuning the protecting polymer shell structural properties. Gold nanoparticles grafted with thermosensitive polymers with a large range of molecular masses and different degrees of hydrophobicity are synthesized by “grafting-to” technique. SANS is employed to characterize the protecting polymer shell structural properties. The absorption spectra are modeled using the Mie Dipolar theory. It is shown that the gold nanoparticle sensitivity to external solvent is progressively reduced with increasing polymer volume fraction of the nanocomposite until the SPR is frozen by the polymer shell. In this case, the SPR mode becomes insensitive to the dielectric properties of the solvent. SPR is also red-shifted (a color change occurs) by thermally inducing the collapse of the polymer shell. The temperature and the extent of the red-shift are controlled by the graft polymer hydrophobicity and salinity. An important part of this thesis is also dedicated to the polymer-protected gold nanoparticles behaviour at the air-water interface. The Langmuir balance technique is used to build interfacial layers whose interparticle distance is modulated by compression, polymer graft chain length and temperature. The interfacial layer structural properties are determined by studying both the polymer graft layer conformation and the gold core organization with neutron and X-ray reflectivities. These reflectivitity measurements also enable us to evaluate and ameliorate the surface layers stability for a better control of the interparticle distance that is important for optimizing the SPR of the surface layer.
33

Morphologie et propriétés élastiques de phases hexatiques dans des films monomoléculaires d'acides gras

Rivière-Cantin, Sophie 17 January 1995 (has links) (PDF)
Cette thèse présente une étude de films monomoléculaires d'acides gras à l'interface eau-air, principalement par microscopie à l'angle de Brewster. Cette technique permet l'observation directe des coexistences de phases lors de transitions de phases du premier ordre; de plus elle est sensible à l'anisotropie optique des films. La première partie contient une étude du diagramme de phase des acides gras, qui comporte des mésophases analogues aux phases de cristaux liquides smectiques. Nous avons montré que lors des transitions de phases entre phases denses, la texture (l'arrangement moléculaire)des phases est réversible et nous avons obtenu des informations sur l'ordre des transitions. Nous avons aussi mis en évidence, dans deux phases constituées de molécules verticales, une très faible anisotropie optique due à la forme rectangulaire du réseau moléculaire. Nous avons ensuite étudié une film d'acide myristique adsorbé à la surface d'une solution aqueuse d'acide myristique. Nous avons observé des domaines d'une mésophase "inclinée" contenant des lignes de défauts d'orientationmoléculaire présentant des fluctuations thermiques. La mesure de leur amplitude a permis de déterminer la tension de ces lignes. Nous nous sommes aussi intéressés aux constantes élastiques qui gouvernent la forme et la texture à l'équilibre des domaines de mésophase. Nous avons d'une part déterminé la tension de ligne de l'interface entre une phase liquide et une mésophase "inclinée" en étudiant la forme des domaines. Celle-ci résulte de l'équilibre entre la tension de ligne, qui favorise des domaines circulaires, et les interactions répulsives à longue portée entre dipoles moléculaires, qui forment les domaines. Des mesures de potentiel de surface ont permis de calculer l'intensité des forces dipolaires. d'autre part, la texture d'autre domaines de cette mésophaseinclinée nous a renseigné sur la valeur du rapport entre l'élasticité de courbure de la direction moléculaire et l'anisotropie de la tension de ligne.
34

Microscopie à l'angle de Brewster : transitions de phases et défauts d'orientation dans des films monomoléculairess

Hénon, Sylvie 11 March 1993 (has links) (PDF)
La microscopie à l'angle de Brewster est une nouvelle et tres puissante technique d'étude des films monomoléculaires à la surface de l'eau. Son principe est basé sur les propriétés de réflectivité des interfaces. Elle est sensible à l'épaisseur, la densité et l'anisotropie optique des films. Cette technique a été appliquée à l'étude de couches adsorbées à la surface de solutions aqueuses d'acides gras (acides palmitiques et myristiques). Ces couches traversent pendant leur formation des transitions de phases. Le nombre, la nature et la morphologie de ces phases dépendent de nombreux paramètres dont le pH. Nous avons entre autres observé des phases optiquement anisotropes, contituées de molécules inclinées par rapport à la normale à la solution.Ces phases sont sans doute des mésophases "verrouillées", c'est à dire que la direction des molécules est fixée par rapport aux directions intermoléculaires. Elles présentent différents types de défauts d'orientation, dont des structures en étoile. L'existence de telles structures est expliquée par application d'un modèle d'élasticité continue développé pour l'étude des films minces de cristaux liquides smectiques. Des structures en zig-zag, en spirales et en bandes de largeur déterminée ont également été observées. Nous avons également étudié les couches d'un polymère (le PDMS) à la surface de l'eau. Nous y avons observé la séparation latérale en domaines de densités de surface différentes, à la fois dans le régime monocouche et le régime multicouches.
35

Interação entre modelos de membrana biológica e poluentes emergentes / Interaction between biological membrane models and emerging pollutants

Maximino, Mateus Dassie [UNESP] 23 February 2018 (has links)
Submitted by Mateus Dassie Maximino (mateusmaximino23@gmail.com) on 2018-04-23T13:55:51Z No. of bitstreams: 1 Dissertação Mestrado - Mateus Dassie Maximino.pdf: 5933036 bytes, checksum: 96040f746ca01578e5036f01f3d89e6e (MD5) / Approved for entry into archive by Claudia Adriana Spindola null (claudia@fct.unesp.br) on 2018-04-23T14:37:07Z (GMT) No. of bitstreams: 1 maximino_md_me_prud.pdf: 5933036 bytes, checksum: 96040f746ca01578e5036f01f3d89e6e (MD5) / Made available in DSpace on 2018-04-23T14:37:07Z (GMT). No. of bitstreams: 1 maximino_md_me_prud.pdf: 5933036 bytes, checksum: 96040f746ca01578e5036f01f3d89e6e (MD5) Previous issue date: 2018-02-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho trata do estudo da interação entre os poluentes emergentes amoxicilina (AMX) e azul de metileno (AM) com modelos-simples de membrana biológica compostas de fosfolipídios zwiteriônicos (DPPC e DOPC), através de filmes de Langmuir e vesículas unilamelares gigantes (GUVs). As membranas foram expostas aos poluentes de forma individual e também misturados (MIX) para que se aproximasse de uma situação real, neste caso, o chamado efeito coquetel, no qual os poluentes são encontrados misturados no ambiente. O objetivo principal foi investigar as possíveis interações entre os poluentes e os fosfolipídios e os consequentes efeitos nas membranas. Nos filmes de Langmuir, as isotermas π-A (pressão superficial por área molecular média) de DPPC revelaram que a AMX e o AM são expulsos da interface ar-água conforme a fase condensada é atingida. O DOPC demonstrou ser menos afetado pela AMX, uma vez que a isoterma não apresentou deslocamento. Contudo, o DOPC se mostrou mais susceptível a interagir com o AM, visto que um deslocamento significativo foi observado. Para ambos os lipídios a MIX causou maiores efeitos, evidenciados por deslocamentos maiores nas isotermas. Análises de módulo compressional mostraram um pequeno aumento na fluidez do filme de DPPC, não observado para o DOPC. As medidas de microscopia de ângulo de Brewster (BAM) na presença dos poluentes revelaram mudanças na morfologia dos filmes, afetando a formação dos domínios de DPPC e impedindo a formação dos mesmos nas monocamadas de DOPC. Os espectros de PMIRRAS para o DPPC indicaram possíveis interações eletrostáticas dos poluentes com a cabeça polar do lipídio, assim como uma desordem na região da sua cauda apolar. A monocamada de DOPC foi bastante afetada pois ocorreram mudanças nas vibrações de quase todos os grupos químicos do lipídio, apresentando inclusive mudanças na região da cauda do lipídio. Os espectros de emissão da sonda LAURDAN nas LUVs revelaram um aumento da rigidez para ambos os lipídios, diferentemente do observado pelas análises de elasticidade da monocamada de Langmuir. As GUVs para ambos os fosfolipídios, ao contrário das monocamadas, apresentaram maior efeito sobre os poluentes aplicados de forma individual, visto que para os poluentes avaliados individualmente foram observados a perda de contraste de fase para os lipídios na presença do AM, assim como mudanças na estabilidade para as GUVs de DOPC em AMX. Tais efeitos não foram observados para a MIX, devido as diferenças estruturais dos modelos de membrana. / The present work is about the interaction between the emerging pollutants amoxicillin (AMX) and methylene blue (MB), with biological membrane models of zwitterionic phospholipids (DPPC and DOPC), through Langmuir films and giant unilamellar vesicles (GUVs). The membrane was exposed to the presence of the pollutants individually, still being performed the analysis with the mixture (MIX) of both in order to get closer to a real situation, in which the pollutants are found mixed in the environment. The main goal was to investigate the possible interactions between the pollutants and phospholipids. The π-A (surface pressure by mean molecular area) isotherms of DPPC reveal that in the condensed phase the lipid expelled the AMX and MB of the air-water interface. The DOPC showed to be less affected by the AMX, once the isotherm did not present a displacement. However, the DOPC showed to be more susceptible to interact with the MB, since significant displacements were observed. In both lipids, the MIX showed to be more effective, causing bigger displacements. The analysis of compressional modulus showed a small increase of the fluidity of the DPPC film, which was not observed to the DOPC. The Brewster Angle Microscopy (BAM) measurements in the presence of the pollutants revealed changes in the morphology, affecting the domains formation of DPPC and inhibiting the formation of the same in monolayers. The PM-IRRAS specters to the DPPC indicated possible electrostatic interactions with the head, as well as a disorder in the tail. The DOPC monolayer was quite affected because there have been changes in almost all chemical groups of lipid, including changes in the tail region of the lipid. The emission spectrum from the dye LAURDAN in the LUVs revealed an increase in the rigidity for both lipids, different from the observed in the analysis of elasticity in the Langmuir monolayers. The GUVs for both phospholipids, unlike the monolayers, showed a major effect on the pollutants applied individually since that were observed losses of phase contrast for the lipids in the presence of MB, such as changes in the stability of the DOPC GUVs in AMX. Such effects were not observed in the MIX, due to the structural differences in the membrane models.
36

Estudo de filmes de Langmuir e Langmuir-Blodgett de aminas anfifílicas utilizando a espectroscopia SFG / The interaction of water with Langmuir films of amphiphilic amines as a function of pH probed by Pi-A isotherms and SFG spectroscopy

Thiers Massami Uehara 24 February 2010 (has links)
O estudo da interação de moléculas orgânicas com a água é de grande importância para diversas áreas das ciências, como por exemplo, na compreensão de sistemas biológicos. Uma elevada diversidade de estudos nesta área já foram realizados, no entanto, alguns aspectos do estudo de filmes finos de aminas anfifílicas não foram satisfatoriamente esclarecidos. Este trabalho aborda filmes de Langmuir de octadecilamina em função do pH e da força iônica de subfases aquosas, investigando a estrutura da monocamada orgânica e sua interação com a água, em diversos graus de ionização. Foi utilizada a Espectroscopia Vibracional por Geração de Soma de Frequências (Sum Frequency Generation - SFG), uma técnica que utiliza o princípio da óptica não-linear para estudar superfícies e interfaces, com o objetivo de investigar a conformação molecular dos filmes de Langmuir de aminas anfifílicas de cadeias longas, seu grau de ionização e a estrutura da água interagindo com a monocamada orgânica. Pôde-se acompanhar a ionização da monocamada em função do pH da subfase pela intensidade do modo de estiramento do grupo NH3+, e verificou-se que ela depende do pH local da interface, que por sua vez é alterado pela ionização da monocamada e é sensível à força iônica da subfase. A água interage com a monocamada via ligações de H com os grupos NH2/NH3+ e forma uma camada com alto grau de orientação perpendicular à superfície, mas relativamente desordenada do ponto de vista da rede de ligações de H (como na água líquida). A conformação das cadeias alquila depende da ionização do filme de Langmuir, sendo bastante compacta e ordenada a altos pHs (filme neutro) e mais expandida e desordenada a baixos pHs. Além disso, foram fabricados filmes de Langmuir-Blodgett (LB) de octadecilamina para comparar a estrutura dos filmes na superfície da água e em substratos sólidos. / The study of the interaction of organic molecules with water is of great importance for many areas of science, such as the understanding of biological systems. A large diversity of studies in this area have been performed, however some aspects of the study of thin films of amphiphilic amines have not been satisfactorily clarified. This dissertation focuses on Langmuir films of Octadecylamine as a function of pH and ionic strength of the aqueous subphase, investigating the structure of the organic monolayer and its interaction with water at various degrees of ionization. Sum-Frequency Vibrational Spectroscopy (SFG spectroscopy), a non-linear optical technique to study surfaces and interfaces, was used in order to investigate the molecular conformation of the Langmuir films, its degree of ionization and the structure of water interacting with the organic monolayer. The monolayer ionization could be monitored by the intensity of the NH3+ group stretch mode, and it was found that it depends on the local pH at the interface, which in turn is changed by the monolayer ionization and is sensitive to the subphase ionic strength. Water interacts with the monolayer by H bonds with NH2/NH3+ groups, forming a layer with a high degree of orientational order along the surface normal, but relatively disordered regarding the H-bonding network (like in the bulk liquid). The conformation of the alkyl chains depends on the monolayer ionization, being compact and all-trans at high pHs, but more expanded and disordered at low pHs. In addition, Langmuir-Blodgett (LB) films of Octadecylamine were fabricated to compare their structure on the solid substrate to those on the water surface
37

Génération de second harmonique sur des films moléculaires chiraux / Second harmonic generation on chiral molecular films

Bruyère, Aurélie 01 December 2016 (has links)
Le manuscrit présente une étude de la réponse non linéaire de films moléculaires chiraux. Ces recherches s'inscrivent dans le contexte général d'une meilleure compréhension de la brisure de symétrie dans les films moléculaires et l'apparition de la chiralité. Ces systèmes moléculaires laissent envisager des perspectives intéressantes notamment le développement d'une nouvelle technologie de guides optiques chiraux.Dans un premier temps, la description des systèmes moléculaires, la fabrication des films ainsi que la modélisation de la réponse non linéaire sont présentées. Dans une seconde partie, les études menées sur des monocouches moléculaires formées sur une interface liquide ont démontré la possibilité de suivre la transition entre une chiralité intrinsèque à la molécule vers une chiralité supramoléculaire induite par une compression mécanique de la monocouche. Il s'avère que ce processus est réversible si la compression du film n'est pas maintenue. Dans une troisième partie, l'analyse du signal optique non linéaire provenant de films solides minces a mis en avant la présence d'une structuration et d'une orientation particulière des molécules dans ce film / The manuscript presents a study of the nonlinear response of chiral molecular films. This research is within the general context of a better understanding of the symmetry breaking in molecular films and the emergence of chirality. These molecular systems presage interesting perspectives including the development of a new chiral optical guides technology.Initially, we describe molecular systems, films formation as well as the modeling of the nonlinear response. In the second part, studies of molecular monolayers formed on a liquid interface demonstrated the ability to monitor the transition between intrinsic chirality of molecule to a supramolecular chirality induced by mechanical compression of the monolayer. It turns out that this process is reversible if the films compression is not maintained. In the third part, the analysis of the nonlinear optical signal from thin solid films bring out the presence of a particular structure and orientation of molecules in the film
38

FORMULATION, CHARACTERIZATION, AND IN VIVO EVALUATION OF A FIRST-IN-KIND POLYMER LUNG SURFACTANT THERAPY

Daniel J Fesenmeier (17456670) 27 November 2023 (has links)
<p dir="ltr">The recent COVID-19 pandemic has emphasized the risk of respiratory infections leading to acute respiratory distress syndrome (ARDS). A significant factor contributing to poor ARDS outcomes is the impairment of lung surfactant due to infiltrating surface-active proteins and phospholipases during lung inflammation. Lung surfactant's vital role in stabilizing alveoli by reducing air-water interfacial tension becomes evident as its dysfunction severely compromises respiratory function. Although lung surfactant (LS) replacement therapy effectively addresses neonatal LS deficiencies, its efficacy in ARDS treatment for adults remains limited. The challenge lies in the chemical similarity between current animal-extracted surfactants and human lung surfactant which are both phospholipid-based. To address this issue, this dissertation outlines a transformative "polymer lung surfactant (PLS)" designed to overcome the limitations of conventional exogenous surfactants in treating ARDS.</p><p dir="ltr">Firstly, a formulation method, referred to as equilibration-nanoprecipitation (ENP), is established which achieves reproducibility, controls sizing, and limits dispersity of the PLS formulation consisting of block copolymer (BCP) kinetically "frozen" micelles/nanoparticles suspended in water. The method uses a two-step approach of 1) equilibrating the BCP nanoparticles in a water/co-solvent mixture and 2) removing co-solvent using dialysis against a large water reservoir. Comparison of ENP with a conventional solvent-exchange technique through experimental and computational analysis yields further insights into ENP's advantages.</p><p dir="ltr">Next, various studies are highlighted which provide fundamental characterizations of the air-water surface behavior and physical properties of BCP nanoparticles in water. The air-water surface properties of block copolymers have been studied extensively when spread as free chains in organic solvent; however, little was previously known about air-water interfacial behavior of water-spread polymer nanoparticles. The studies address such topics as the effect of nanoparticle size, effect of nanoparticle core chemistry, and the effect of temperature on surface-mechanical behavior. Insights into nanoparticle molecular structure at the interface are provided through X-ray reflectivity and grazing incidence X-ray diffraction. The effect of temperature is further characterized by developing novel NMR and Langmuir trough methods to determine the physical state (glassy vs rubbery) of the core domain in the nanoconfined state at temperatures above and below physiologic temperature.</p><p dir="ltr">Lastly, <i>in vivo </i>studies are presented which demonstrate the detailed and promising proof-of-concept results on the efficacy of the PLS technology in mouse models of lung injury. The PLS therapy not only improves biomechanical function of the lung, but it also significantly lowers the extent of lung injury as shown by histological analysis and inflammatory marker measurements. An additional <i>in vivo </i>study is presented which highlights challenges in the delivery of the liquid PLS suspension to the lungs. The <i>in vivo </i>studies ultimately provide solid motivation for continued research into the development of the PLS therapy.</p><p dir="ltr">Given the promising potential of the PLS technology shown in the <i>in vivo</i> studies, the materials characterizations shared in this presentation offer valuable insights into the design of a novel PLS therapy. From these insights, key design parameters such as nanoparticle size characteristics, core chemistry, and core molecular weight can be chosen to produce the most desirable material properties. Overall, this dissertation furthers the progress of PLS therapeutic development and will hopefully ultimately contribute to improved health outcomes in patients suffering from ARDS.</p>
39

Estudo de agregados de moléculas fosfolipídicas em superfície sólida para simulação de membranas biológicas / Study of phospholipidic molecule aggregates on a solid surface for simulation of biological membranes

Gomide, Andreza Barbosa 03 January 2011 (has links)
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
40

Self-assembly of Fatty Acids of Hair at the water-air interface

Batista, Marine January 2020 (has links)
18-methyl eicosanoic acid (18-MEA), which is a branched fatty acid, is found at the outermost surface of mammalian hair with other straight-chain fatty acids such as palmitic acid and stearic acid. However, the precise role of 18-MEA is not yet completely understood. 18-MEA on Cadmium chloride subphase forms curvature at the water/air interface, leading to the formation of 3D-domains that can be easily transferred into solid support allowing to create complex and multi-functional structures. This project investigates if a non-toxic subphase would also lead to the formation of 3D-domains or if it is an intrinsic property of Cadmium chloride; and to investigate if the domain properties were tuneable. A combination of the Langmuir trough and the Atomic Force Microscopy is used. It is shown that a toxic subphase is not necessary and a more benign sodium subphase can be used to obtain 3D-domains. It is also shown that different chains length interact dissimilarly with the branched fatty acid. This results in the formation of very various structures. It is also shown that the subphase, the surface pressure of deposition and the composition of the fatty acid in the monolayer affect the properties of the domain, leading to different size of domain but also different morphology in the domain. Circular domains, elongated domains, continuous labyrinthine structures, dendritic centipede-like structures and no domains are obtained. / På den yttersta ytan av däggdjurshår återfinns den grenade fettsyran 18-methyleikosansyra tillsammans en mindre mängd av de raka fettsyrornapalmitinsyra och stearinsyra. Den exakta rollen av 18-MEA är dock ännu inte heltklarlagd. Ett monoskikt av 18-MEA på en subfas innehållande kadmiumklorid påtvingar en krökning av vatten–luftgränsytan. Det leder till bildandet av 3D-domäner som lätt kan överföras från vattenytan till fasta ytor vilket möjliggör att dekorera dessa ytor med komplexa och multifunktionella strukturer. Detta projekt undersöker om andra, miljövänliga motjoner i subfasen också skulle leda till bildandet av 3D-domäner eller om det är en inneboende egenskap hos kadmiumklorid. Det här ger även insikt om hur motjoner kan användas för att påverka och kontrollera domänbildningen. En kombination av Langmuirtråg och atomkraftsmikroskopi används för att karakterisera monoskikten. Det visas att en subfas innehållande kadmium inte är nödvändig och att en mer miljövänlig natriumsubfas kan användas för att bilda 3D-domäner. Det visas också att olika kedjors längd interagerar olika med den grenade fettsyran 18-MEA, vilket resulterar i bildandet av olika strukturer i deponerade monoskikt. Det visas också att yttrycket vid deponering och sammansättningen av fettsyror i mono skiktet påverkar egenskaperna hos monoskiktet, vilket leder till varierande storlek och struktur på de bildade domänerna, där cirkulära och långsträckta domäner, kontinuerliga labyrintstrukturer och dendritiska tusenfotingsliknande strukturer observeras.

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