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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.
101

Processing and Gas Barrier Behavior of Multilayer Thin Nanocomposite Films

Yang, You-Hao 2012 August 1900 (has links)
Thin films with the ability to impart oxygen and other types of gas barrier are crucial to commercial packaging applications. Commodity polymers, such as polyethylene (PE), polycarbonate (PC) and polyethylene terephthalate (PET), have insufficient barrier for goods requiring long shelf life. Current gas barrier technologies like plasma-enhanced vapor deposition (PECVD) often create high barrier metal oxide films, which are prone to cracking when flexed. Bulk composites composed of polymer and impermeable nanoparticles show improved barrier, but particle aggregation limits their practical utility for applications requiring high barrier and transparency. Layer-by-layer (LbL) assemblies allow polymers and nanoparticles to be mixed with high particle loadings, creating super gas barrier thin films on substrates normally exhibiting high gas permeability. Branched polyethylenimine (PEI) and poly (acrylic acid) (PAA) were deposited using LbL to create gas barrier films with varying pH combinations. Film thickness and mass fraction of each component was controlled by their combined charge. With lower charge density (PEI at pH 10 and PAA at pH 4), PEI/PAA assemblies exhibit the best oxygen barrier relative to other pH combinations. An 8 BL PEI/PAA film, with a thickness of 451 nm, has an oxygen permeability lower than 4.8 x 10^-21 cm^3 * cm/cm^2 * s * Pa, which is comparable to a 100 nm SiOx nanocoating. Crosslinking these films with glutaraldehyde (GA), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide (EDC) or heating forms covalent bonds between PEI and/or PAA. Oxygen transmission rates (OTR) of 8 BL films crosslinked with 0.1M GA or 0.01M EDC show the best oxygen barrier at 100% RH. Graphene oxide (GO) sheets and PEI were deposited via LbL with varying GO concentration. The resulting thin films have an average bilayer thickness from 4.3 to 5.0 nm and a GO mass fraction from 88 to 91wt%. Transmission electron microscopy and atomic force microscopy images reveal a highly-oriented nanobrick wall structure. A 10 BL PEI/GO film that is 91 nm thick, made with a 0.2 wt% GO suspension, exhibits an oxygen permeability of 2.5 x 10^-20 cm^3 * cm/cm^2 * s * Pa. Finally, the influence of deposition time on thin film assembly was examined by depositing montmorillonite (MMT) or laponite (LAP) clays paired with PEI. Film growth and microstructure suggests that smaller aspect ratio LAP clay is more dip-time dependent than MMT and larger aspect ratio MMT has better oxygen barrier. A 30 BL PEI/MMT film made with 10 second dips in PEI has the same undetectable OTR as a film with 5 minute dips (with dips in MMT held at 5 minutes in both cases), indicating LbL gas barrier can be made more quickly than initially thought. These high barrier recipes, with simple and efficient processing conditions, are good candidates for a variety of packaging applications.
102

Nanocristais de celulose bacteriana carboximetilada como poliÃnion na preparaÃÃo de complexos polieletrolÃtico / Carboxymethylated bacterial cellulose nanocrystals as polyanion for polyelectrolyte complex preparation.

NiÃdja Fittipaldi Vasconcelos 11 February 2015 (has links)
CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / O presente trabalho teve como objetivo obter nanocristais de celulose bacteriana carboximetilada (NCCBC) e avaliÃ-los como poliÃnion na preparaÃÃo de complexos polieletrolÃticos (CEPs). Para obtenÃÃo dos nanocristais de celulose bacteriana (NCCB), procedeu-se à hidrÃlise Ãcida, investigando o uso de Ãcido sulfÃrico (H2SO4), em diferentes concentraÃÃes e tempos de reaÃÃo, bem como sua combinaÃÃo com Ãcido clorÃdrico (HCl). Foram avaliados dois tipos de solventes alcoÃlicos na carboximetilaÃÃo: etanol e o isopropanol. Os CEPs foram sintetizados utilizando os nanocristais funcionalizados (NCCBC) e quitosana (QT), sendo investigados dois parÃmetros: a razÃo de cargas (n+/n- = 0,5, 1 e 5) e a ordem de adiÃÃo dos polieletrÃlitos (QT/NCCBC e NCCBC/QT). De acordo com os resultados obtidos, todas as suspensÃes de NCCB apresentaram valores de potencial Zeta superiores à 30 mV (em mÃdulo), indicando boa dispersÃo em meio aquoso, e Ãndices de cristalinidade (Ic) superior ao da celulose bacteriana (CB), indicando remoÃÃo de conteÃdo amorfo. O uso combinado dos Ãcidos favoreceu a obtenÃÃo de NCCB mais estÃveis termicamente sem, contudo, comprometer sua cristalinidade e seu potencial Zeta. As melhores condiÃÃes foram obtidas utilizando 50% (m/m) de H2SO4 por 1 hora de reaÃÃo (Experimento 1) e 60% (m/m) de H2SO4 e 36,5% (m/m) de HCl por 1 hora (Experimento A). O uso do isopropanol, na reaÃÃo de carboximetilaÃÃo, promoveu a obtenÃÃo de NCCBC com maior valor do grau de substituiÃÃo (GS). A funcionalizaÃÃo melhorou o carÃter hidrofÃlico e aumentou as cargas negativas na superfÃcie dos NCCBC. Em relaÃÃo aos complexos polieletrolÃticos, os NCCBC desempenharam o papel de promissor poliÃnion, sendo possÃvel preparar CEPs com tamanho das partÃculas, variando entre 276 a 588 nm e potencial Zeta, no intervalo de -24,23 a +39,02 mV. Do ponto de vista de aplicaÃÃo, os CEPs obtidos com potencial Zeta negativo podem ser considerados promissores para elaborar materiais com propriedades antitrombogÃnicas e anticalcificante. / The aim of this work was to produce carboxymethylated bacterial cellulose nanocrystals (CBCNC) and to evaluate them as a polyanion to be used in the preparation of polyelectrolyte complex (PEC). Bacterial cellulose nanocrystals (BCNC) were extracted by sulfuric acid hydrolysis, evaluating different concentration, time of reaction, and combination with hydrochloric acid. Carboxymethylation reaction was performed in two different solvents: ethanol and isopropanol. PECs were synthetized with the combination of CBCNC and chitosan (Ch), varying two parameters: charge ratio (n+/n- = 0.5, 1.0, and 5.0), and the addition sequence of the polyelectrolytes in the reaction medium (Ch/CBCNC or CBCNC/Ch). All extracted nanocrystals presented Zeta potential values higher than 30 mV (in modulus), an indicative of good dispersivity in aqueous medium, and crystallinity index higher than the original bacterial cellulose index, an indicative of amorphous content elimination. Combination of acids yielded BCNC crystals thermally more stable without crystallinity index loss, neither Zeta potential modulus reduction. Optimized extraction conditions included sulfuric acid hydrolysis (50% H2SO4 (w/w), 60 min of reaction â Experiment 1) and sulfuric acid : hydrochloric acid hydrolysis (60% H2SO4 (w/w) : 36.5% HCl (w/w), 60 min of reaction â Experiment A). The highest substitution degree in the carboxymethylation reaction was achieved in isopropanol. The functionalization improved the hydrophylicity and the negative surface charges in the BCNC. CBCNC was a suitable polyanion to produce PEC, which presented particle size ranging from 276 to 588 nm and Zeta potential ranging from -24.33 to +39.02 mV. Negatively charged PEC may be used to prepare anti-thrombogenic and anti-calcifying materials.
103

Autoassociação de sais complexos de surfatantes e copolímeros aleatórios e enxertados / Self-assembly of complex salts formed by surfactants and random or grafted copolymers

Silva, Ana Maria Percebom Sette da, 1986- 21 August 2018 (has links)
Orientador: Watson Loh / Texto em português e inglês / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:28:37Z (GMT). No. of bitstreams: 1 Silva_AnaMariaPercebomSetteda_D.pdf: 24339728 bytes, checksum: 5607616747acea067ac22294eb185712 (MD5) Previous issue date: 2012 / Resumo: Este trabalho se insere em uma linha de pesquisa de nosso grupo sobre a autoassociação de surfatantes iônicos que são neutralizados por contraíons poliméricos, formando os chamados sais complexos. A proposta do presente projeto trata da verificação do efeito de diferentes arquiteturas ou composições químicas de poliânions sobre as propriedades de autoassociação do surfatante catiônico hexadeciltrimetilamônio, utilizando copolímeros aleatórios. A mistura estequiométrica de poli-íons e surfatantes opostamente carregados geralmente leva à separação de uma fase concentrada em sal complexo. Esta fase pode apresentar diferentes estruturas (cristais líquidos ou sistemas micelares) e é interessante para aplicações como moldes para matérias mesoporosos e alguns cosméticos, mas inviabiliza o seu uso em soluções aquosas, como por exemplo, para carreadores de fármacos. Para evitar a separação de fases de sais complexos em água, a estratégia utilizada neste trabalho foi usar copolímeros que possuem comonômeros aniônicos e cadeias laterais hidrofílicas. Dentro do contexto de se estudar complexos de copoli-íons, este projeto também envolve o estudo de sais complexos formados por um copolímero que possui comonômeros hidrofóbicos e hidrofílicos, para verificar seu efeito sobre o comportamento de fases. Para identificar e caracterizar as fases formadas, a principal técnica usada foi a de espalhamento de raios-X a baixos ângulos, que permitiu determinar os diagramas de fases. Também permitiu, em conjunto com o resultado de outras técnicas (espalhamento de luz dinâmico, difusão por ressonância magnética nuclear, tensiometria e fluorescência), mostrar que alterações na estrutura dos polímeros diversifica as estruturas formadas pela autoassociação do surfatante e, consequentemente, suas propriedades / Abstract: This project is part of a research in our group involving the selfassembly of ionic surfactants neutralized by polymeric counterions, forming the so-called complex salts. The main goal of this study is to verify the effect of different architectures or different chemical compositions of polyanions on the self-assembly of the cationic surfactant hexadecyltrimethylammonium, by using different random copolymers. The stoichiometric mixture of poly-ions and oppositely charged surfactants generally leads to the separation of a phase concentrated in complex salt. This phase can display different structures (liquid crystal or micellar systems) and is interesting for applications such as templates for mesoporous materials or cosmetics, but forbids the use in aqueous solutions, such as for drug carriers. To avoid phase separation of complex salts in water, the strategy was to use copolymers with anionic comonomers and hydrophilic neutral side-chains. In the context of studying complex salts of copolyions, this project also involves the study of complex salts formed by a copolymer with both hydrophilic and hydrophobic comonomers, to verify the effect on the phase behavior. In order to identify and characterize the obtained phases, the main technique used was small angle X-ray scattering, which provided information to determine the phase diagrams. These data along with the results from other techniques (dynamic light scattering, nuclear magnetic resonance, surface tension measurements and fluorescence) show that changes on the polymer structure provide a diversification of the surfactant assembles and, as a consequence, of the resulting properties / Doutorado / Físico-Química / Doutora em Ciências
104

Mechanically micropatterned polyelectrolyte multilayers to control cell behavior / Multicouches de polyélectrolytes aux propriétés mécaniques spatialement contrôlées : étude de cellules eucaryotes et procaryotes

Saha, Naresh 18 December 2013 (has links)
Les films polyélectrolytes ont émergé comme un outil polyvalent dans le domaine desbiomatériaux et de l’ingénierie tissulaire. Dans cette étude, nous avons conçu des films à base debiopolymère, dont la rigidité peut être modulée par photo-réticulation. L’adhésion de bactéries etde cellules mammifères sur ces films a été étudiée. Une telle manipulation de rigidité superficielleconduit à une réponse différentielle des bactéries et des cellules mammifères. Les bactéries àGram négatif présentent une meilleure croissance sur des films nous alors que les cellulesmammifères préféraient les films plus rigides. Ces films ont été spatialement structurés à l’aided’un photomasque, permettant de créer des zones adjacentes de rigidité variable et de formecontrôlée. Les motifs photostructurés ont conduit les cellules à s’organiser préférentiellement surles zones les plus rigides. Une étude comparative a été réalisée avec des micropatronsbiochimiques. Les résultats ont montré des réponses similaires pour trois types cellulairesdifférents. Ces films offrent des perspectives intéressantes pour l’ingénierie tissulaire et pour letest de médicaments. / Polyelectrolyte multilayers have emerged as a versatile tool in the field of biomaterials and tissueengineering. In this study, photocrosslinkable polyelectrolyte films based on biopolymers whosestiffness can be easily tuned by UV irradiation were prepared. Then, they were tested againstbacteria and mammalian cells to address the influence of the film stiffness on cell behavior. Suchsuperficial stiffness manipulation resulted in differential response of bacteria and mammaliancells. Gram negative bacteria evidenced better growth on softer films while various mammaliancells preferred stiffer films. Stiffness patterns of various geometries and sizes were generated byexposing the films to the UV light through a photomask incorporated in transparent substrates.The patterned films composed of stiff motifs distributed in a soft background induced apreferential spatial organization, which depended on pattern shape and size. A comparative studywith commercial biochemical patterns revealed similar pattern fidelity for three differentmammalian cell types. Such mechanical patterns on a 2D film appear promising for futureapplications in tissue engineering or for drug screening.
105

Floculation - Formation et structure des agrégats entre les chaînes de polyélectrolytes et colloïdes argileux / Flocculation - Formation and structure of aggregates composed of polyelectrolyte chains and clay colloidal particles

Sakhawoth, Yasine 03 October 2017 (has links)
La floculation est un procédé que l’on peut retrouver dans plusieurs applications au niveau industriel comme la fabrication du papier ou le traitement de l’eau. Il est nécessaire de comprendre la formation et la structure des agrégats floculés pour maîtriser et optimiser un tel procédé. La plupart des études sur la floculation implique des particules sphériques, impliquant ainsi un manque de connaissance sur la floculation de particules anisotropes comme par exemple des plaquettes de colloïdes argileux. C’est pour cela que dans cette étude, j’ai étudié la floculation d’une suspension d’argile type Montmorillonite dans l’eau par des polyélectrolytes cationiques modèles appelés ionènes. En utilisant ce système modèle, il est possible d’étudier l’effet de la densité de charges des ionènes, la taille des plaquettes d’argile ou encore la longueur des chaînes sur le mode de floculation et l’arrangement des chaînes et des plaquettes au sein des agrégats. Dans un premier temps, l’effet de la densité de charge des polyélectrolytes sur l’efficacité de floculation a été étudié en combinant des mesures de turbidité et de potentiel zêta. Ces mesures ont permis de montrer que la densité de charge des ionènes influence le mode de floculation et les conditions de floculation optimale. La conformation des chaînes dépend de la densité de charge des ionènes et c’est pour cela que j’ai poursuivi l’étude par des mesures de diffusion de rayonnement aux petits angles afin de pouvoir corréler l’effet de la conformation des chaînes avec la structure des agrégats à différentes échelles. La diffusion des rayons X aux petits angles a permis de montrer la présence d’organisation des plaquettes sous forme d’empilement face-face. Ensuite, cette technique a permis de souligner l’effet de la densité de charge sur la distance entre plaquettes dans les empilements. Pour les ionènes les moins chargés, la formation de boucles de chaînes des ionènes entre les faces d’argile induit les distances entre plaquettes les plus grandes au sein des agrégats. Les différences de conformations des différents ionènes ont été confirmées par diffusion de neutrons aux petits angles. Cette technique, sous la condition de variation de contraste, permet de sonder uniquement les chaînes dans les agrégats. J’ai également étudié le comportement des différents ionènes en solution aqueuse en absence des particules d’argile par diffusion de neutrons aux petits angles et RMN. Dans le domaine des hautes concentrations, ces systèmes montrent clairement des différences d’interaction entre les chaînes en fonction de la nature des contre-ions. L’évolution de ces interactions suit parfaitement la série de Hofmeister. / Flocculation is a key process in numerous environmental and industrial technologies such as purification of waste-water or paper making. It is necessary to understand the formation and structure of the aggregates to control and optimize such a process. Most of the studies on flocculation involve spherical particles, but there is a clear need to understand the flocculation of anisotropic particles such as clay colloids, which are platelets. I studied the flocculation of montmorillonite clay suspensions in water by well-defined cationic polyelectrolytes called ionenes. By using this model system, it is possible to study the effect of relative charge densities and sizes of ionene chains and clay platelets, on the mode of flocculation and their arrangement inside the aggregates formed. Initially, I studied the effect of charge density of polyelectrolytes on the flocculation efficiency of clay platelets, by combining measurements of turbidity and zeta potential. While the aggregates are always ionene-deficient, the charge density of ionenes leads to variations in the mode of flocculation and in the optimum flocculation conditions. The conformation of the ionene chains inside the aggregates depends on the charge density of ionenes and this is why I continued the study by small-angle scattering experiments in order to correlate the conformation of the chains with the structure of aggregates on different spatial scales. Small-angle X-ray scattering showed the presence of platelet stacks in a face-face configuration, demonstrating itself as a clear stacking peak in the scattering spectra. Further, this technique allowed to highlight the effect of the charge density on the interlamellar spacing inside these stacks. For the most weakly charged ionenes, loops of the ionene chains between the faces of adjacent platelets induce a higher interlamellar spacing inside the stacks. The differences of conformation of ionenes are confirmed by small-angle neutron scattering. This technique, under the condition of contrast matching, allows to probe only ionene chains within the aggegates aggregates. On a larger spatial scale, I have observed that by matching closely the charge density on ionene chains and on clay platelets the most compact aggregates are produced. I have also studied the behaviour of the different ionenes in aqueous solution in absence of clay particles by small-angle neutron scattering and NMR. At high chain concentrations, these systems clearly show differences in inter-chain interactions, depending on the nature of their counterions. The evolution of these interactions follows closely the Hofmeister series.
106

Structure et rhéologie du poly(acide méthacrylique) en régime semi-dilué : organisation sous cisaillement et en température / Structure and rheology of poly(methacrylic acid) in the semi-dilute regime : organisation under shear and temperature

Robin, Clément 05 October 2016 (has links)
Le poly(acide méthacrylique) (PMAA) est un polyélectrolyte relativement peu étudié qui présente cependant des caractéristiques physico-chimiques variées et très intéressantes. La présence d'un groupement méthyle en alpha du groupement acide carboxylique lui confère un comportement très différent de son homologue beaucoup plus étudié : le poly(acide acrylique). En solvant aqueux et à faible taux d'ionisation, la synergie entre les interactions hydrophobes provenant des groupements méthyle et les liaisons hydrogène intramoléculaires entre les groupements acides carboxyliques sont à l'origine de la conformation très compacte adoptée par la chaîne polymère. Néanmoins, au-delà d'un taux d'ionisation critique, la chaîne de PMAA adopte une conformation très étendue semblable à celle adoptée par un polyélectrolyte classique à taux de charges élevé. L'objectif principal de ce travail est de relier les propriétés rhéologiques à la structure de solutions semi-diluées de PMAA.Le comportement rhéologique des solutions de PMAA a été étudié en fonction du régime de concentration et du taux d'ionisation. Les solutions semi-diluées suffisamment concentrées de PMAA présentent un comportement antithixotrope lorsque les macromolécules sont dans leur état globulaire. Le cisaillement entraîne la formation de liaisons intermoléculaires à l'origine de la formation d'un gel physique. Cette évolution a été reliée à une valeur de contrainte critique de cisaillement indépendante de la concentration pour laquelle le gel se forme. Ce phénomène présente des caractéristiques analogues à celles observées pour des suspensions colloïdales nanométriques.En solution aqueuse, les chaînes de PMAA non ionisées présentent une température critique inférieure de solubilité (LCST) située autour 67 $^{circ}$C. Une étude de ce phénomène par RMN a permis de sonder la mobilité des molécules d'eau au cours de la transition et de mettre en évidence un phénomène de déshydratation des macromolécules. Des mesures de diffusion de neutrons aux petits angles en température ont également montré la formation d'interfaces entre domaines riches et pauvres en polymère. L'emploi de ces différentes approches expérimentales a permis d'identifier un mécanisme de transition de phase très semblable à celui du poly(N-isopropylacrylamide) (PNIPAM). La température de point de trouble coïncide également avec une température de gel pour laquelle un gel viscoélastique se forme.La compréhension du comportement rhéologique et en température du PMAA est une étude nécessaire préalablement à l'élaboration de nanocomposites à base de PMAA et de nanoparticules de silice. Les nanocomposites sont préparés en solution et la fonctionnalisation des particules de silice permet d'augmenter les interactions polymère/silice. Le choix des groupements fonctionnels greffés à la surface des particules de silice a permis de rendre ces interactions variables par le pH de la solution. Une perspective à ce travail sera de corréler les propriétés structurales du nanocomposite à ses propriétés rhéologiques au cours du séchage / Poly(methacrylic acid) (PMAA) is a polyelectrolyte which has been rather scarcely investigated in the literature, despite its various and very interesting physical properties. The behavior of PMAA solutions is drastically different from the one displayed by the extensively studied poly(acrylic acid), due to the methyl group located in the alpha position of the carboxylic acid function. At low ionization degrees in aqueous solvent, synergetic effects resulting from both hydrophobic interactions (methyl groups) and intramolecular hydrogen bonds between acidic groups are responsible for the hypercoiled conformation of the PMAA chains. Nevertheless, above a critical ionization degree, the PMAA macromolecule behaves as an extended chain similar to a usual highly charged polyelectrolyte. The main purpose of this work is to correlate the rheological properties to the structure of the chains for semi-dilute solutions of PMAA.In the semi-dilute regime, above a critical concentration, PMAA solutions display a sharp increase in their viscosity over time under shear. This phenomenon known as antithixotropy occurs only when the macromolecules adopt a hypercoiled conformation. The influence of both concentration and ionization degree on the rheological behavior of PMAA solutions was studied. Shear induces the formation of intermolecular bonds which are responsible for the formation of a physical gel. We have demonstrated that the critical shear stress at which the gel is formed does not depend on the concentration. Interestingly, the results obtained remind some features observed in the case of the shear thickening of charged colloids.Neutral PMAA chains in water also display a Lower Critical Solution Temperature (LCST) around 67 $^{circ}$C. The reorientational dynamics of water molecules above the LCST was studied by means of NMR experiments, which evidenced the dehydration of the polymer coils during phase separation. The formation of interfaces between polymer-rich and polymer-poor domains was investigated by small-angle neutron scattering experiments. A possible mechanism describing the transition at the molecular level was derived from the results obtained throughout the use of complementary experimental approaches. This mechanism is very similar to the one proposed for the LCST transition of poly(N-isopropylacrylamide) (PNIPAM). The cloud point temperature of PMAA solutions is the same as the gel temperature at which a viscoelastic gel is formed.The understanding of the behavior of PMAA solutions under shear as well as under temperature is an essential prerequisite to the design of PMAA/silica nanocomposites. These nanocomposites were are prepared in the solution state. The interactions between PMAA chains and silica were clearly increased by the functionalization of the silica particles. Such interactions between PMAA and filler particles were found to be related to the pH of the solutions, due to the nature of the chemical groups at the surface of the functionalized silica. A possible perspective to this work would be the correlation between the structural features of the nanocomposites and their rheological properties during the drying process
107

Solvent Effects And Ionic Interactions In Polyaniline Systems

Ghosh, Soumyadeb 05 1900 (has links) (PDF)
No description available.
108

Diffusion von Dithionit in Polyelektrolytmultischichten

Meyer, Stephan 09 June 2015 (has links)
Die vorliegende Arbeit beschreibt die Etablierung einer neuen Methode zur Durchführung von Diffusionsmessungen innerhalb weniger Nanometer dicker Polyelektrolytmultischichten. An das Polykation PAH wurde der Fluorophor NBD gekoppelt. PAH-NBD kann im Rahmen des Beschichtungsprozesses an verschiedene Positionen des auf kolloidalen Teilchen adsorbierten PAH/PSS-Multifilms lokalisiert werden. Nach Dithionitzugabe wird die Fluoreszenz durch die ablaufende Reduktionsreaktion zwischen NBD und Dithionit gelöscht. Die Abnahme der Fluoreszenzintensität wird flowzytometrisch detektiert. Die Auswertung der Daten erfolgte auf der Grundlage verschiedener theoretischer Näherungslösungen für Subdiffusion, gekoppelt mit der Reaktionskinetik der Fluoreszenzlöschung. Die Ergebnisse sind nicht mit normaler Diffusion innerhalb der Schichten vereinbar. Vielmehr ergibt sich eine stark subdiffusive Transportcharakteristik des Dithionits innerhalb des Polyelektrolytmultifilms. Als Ursachen hierfür werden die Wechselwirkungen der Dithionitmoleküle mit den PAH-Molekülen sowie die unterschiedlichen Zugänglichkeiten der NBD-Moleküle für die diffundierenden Dithionitmoleküle durch ständige Konformationsänderungen der PAH-Moleküle angesehen. Hervorzuheben ist, dass erstmalig eine Technik etabliert wurde, mit welcher Diffusionsmessungen auf nanoskopischer Skala innerhalb von Polyelektrolytmultischichten durchgeführt werden können. Die subdiffusive Kinetik ist im Vergleich zu normaler Diffusion stark verzögert und ermöglicht dadurch einen länger anhaltenden Stofftransport, was für die Anwendung der Polyelektrolytmultischichten als Medikamententräger besonders vorteilhaft ist. Es wurde gezeigt, dass die Ladung der obersten Schicht des Polyelektrolytmultifilms einen erheblichen Einfluss auf die Qualität und die Struktur der Polyelektrolytmatrix, und das ebenfalls in tieferen Bereichen der Polyelektrolytmultischicht, hat.
109

Untersuchung der Freisetzungskinetik unterschiedlicher mit rh-BMP-2 beladener Polyelektrolyt-Multilayer-Schichten auf Titanplättchen / Investigation of the release kinetics of different polyelectrolyte multilayer coatings loaded with rh-BMP-2 on titanium platelets.

Baron von Hahn, Nikolaus 26 January 2021 (has links)
No description available.
110

Development of New Bacteria-Reducing Surfaces

Illergård, Josefin January 2009 (has links)
In recent years, antibacterial surfaces have been a subject of increased interest. Especiallyinteresting are non-leaching, contact-active surfaces that physically disrupts the bacterialcell using immobilised cationic polymers. Thus the risks of bacterial resistance and discharge of hazardous biocides is minimised. The assembly of such surfaces is elaborate andusually involves organic solvents. Here, polyelectrolyte multilayers (PEM) are proposed as an effective surface modification method, with an overall goal of producing antibacterial cellulose fibres. The PEM process is based on physical adsorption of oppositely charged polymers in aqueous solutions. Multilayers were formed with the bactericidal polymer polyvinylamine (PVAm) and polyacrylic acid. PVAm compounds with hydrophobic modificationswere applied as well, as they possess increased antibacterial activity in solution. In this work, the multilayer formation was studied on model surfaces of silicone oxide and glass in order to obtain fundamental knowledge of the polymer system. QCM-D and reflectometry, which detect total mass including bound water and polymer mass only, respectively, were used to analyse the layer formation. Salt-concentrations were varied at 1, 10 or 100 mM NaCl. A stepwise multilayer formation with exponential-like polymer adsorption but with decreasing water content for each layer was seen at all salt concentrations.A higher salt concentration resulted in an increased adsorbed mass. No significant differences in adsorption between the modified and unmodified PVAm could be detected. AFM imaging applied to multilayers having nine layers showed large surface aggregates under high salt conditions for the C6-modified PVAm. Dynamic light scattering showed that the polymer occurred as single molecules in solution; hence it was concluded that theaggregation is surface-associated. The multilayers were then tested for bacterial growth inhibition. The relative bacterial inhibition was time-dependent, as the surface was saturated with bacteria over time. After two hours, a maximal inhibition of 99 % could be observed for the multilayers. After eight hours, a moderate inhibition of less than 40 % was detected. Using multilayers affected the results positively compared to single layers. After three layers, though, no further reductionwas seen. Viability staining of the surface-adhered bacteria revealed that the adhered bacteria had intact membranes. Therefore, the microbiological properties of the multilayers can at this point be described more as growth-inhibiting by bacterial adhesion effectsthan as biocidal. However, this work has shown the importance of combining surface characterisation and microbial testing to understand the bacteria-surface interaction. / Biointeractive fibres

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