• Refine Query
  • Source
  • Publication year
  • to
  • Language
  • 43
  • 20
  • 17
  • 11
  • 4
  • 2
  • 1
  • Tagged with
  • 128
  • 40
  • 32
  • 16
  • 16
  • 14
  • 14
  • 12
  • 12
  • 11
  • 10
  • 9
  • 9
  • 9
  • 9
  • 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.
81

PHASE BEHAVIOR OF AMORPHOUS SOLID DISPERSIONS: MISCIBILITY AND MOLECULAR INTERACTIONS

Sarpal, Kanika 01 January 2019 (has links)
Over the past few decades, amorphous solid dispersions (ASDs) have been of great interest to pharmaceutical scientists to address bioavailability issues associated with poorly water-soluble drugs. ASDs consist of an active pharmaceutical ingredient (API) that is typically dispersed in an inert polymeric matrix. Despite promising advantages, a major concern that has resulted in limited marketed formulations is the physical instability of these complex formulations. Physical instability is often manifested as phase heterogeneity, where the drug and carrier migrate and generate distinct phases, which can be a prelude to recrystallization. One important factor that dictates the physical stability of ASDs is the spatial distribution of API in the polymeric matrix. It is generally agreed that intimate mixing of the drug and polymer is necessary to achieve maximum stabilization, and thus understanding the factors controlling phase mixing and nano-domain structure of ASDs is crucial to rational formulation design. The focus of this thesis work is to better understand the factors involved in phase mixing on the nanometric level and get insights on the role of excipients on overall stabilization of these systems. The central hypothesis of this research is that an intimately mixed ASD will have better physical stability as compared to a partially homogeneous or a non-homogeneous system. Our approach is to probe and correlate phase homogeneity and intermolecular drug-excipient interactions to better understand the physical stability of ASDs primarily using solid-state nuclear magnetic resonance (SSNMR) spectroscopy and other solid-state characterization tools. A detailed investigation was carried out to understand the role of hydrogen bonding on compositional homogeneity on different model systems. A comprehensive characterization of ternary ASDs in terms of molecular interactions and physical stability was studied. Finally, long-term physical stability studies were conducted in order to understand the impact of different grades of a cellulosic polymer on phase homogeneity for two sets of samples prepared via different methods. Overall, through this research an attempt has been made to address some relevant questions pertaining to nano-phase heterogeneity in ASDs and provide a molecular level understanding of these complex systems to enable rational formulation design.
82

Film Formation of Water-borne Polymer Dispersion: Designed Polymer Diffusion for High Performance Low VOC Emission Coatings

Soleimani Kheibari, Mohsen 31 August 2012 (has links)
In this thesis, I describe experiments that were designed to provide a better understanding of polymer diffusion during latex film formation. This step leads to the improvement of film mechanical properties. Polymer diffusion in these films was monitored by fluorescence resonance energy transfer. Current paint formulations contain Volatile Organic Compounds (VOCs) as plasticizers to facilitate polymer diffusion. The drawback of this technology is the release of VOCs to the atmosphere. VOCs are deleterious to the environment and contribute to smog and ground level ozone formation. The propensity of water, an indispensible part of any latex dispersion, to promote polymer diffusion was studied. Copolymers of poly (butyl acrylate-co-methyl methacrylate) and poly(ethylhexyl acrylate-co-tertiary butyl methacrylate) with similar glass transition temperatures but different hydrophobicity were compared. Polymer diffusion was monitored for films aged at different relative humidities. Water absorbed by the hydrophobic copolymer film was less efficient in promoting polymer diffusion than in the hydrophilic polymer. Only the fraction of water which is molecularly dissolved in the film participate actively in plasticization. Although water has low solubility in most latex polymers, molecularly dissolved water is more efficient than many traditional plasticizers. The possibility of modifying film formation behavior of acrylic dispersions with oligomers was studied by synthesizing hybrid polymer particles consisting of a high molecular weigh (high-M) polymer and an oligomer with the same composition. Oligomers with lower molecular weight are more efficient as diffusion promoters and have less deleterious effect on high-M polymer viscosity. A different set of hybrid particles were prepared in which the oligomer contained methacrylic acid units. The composition of the oligomer was tuned to be miscible with the high-M polymer when the acid groups were protonated but to phase separate when the acid groups were deprotonated. At basic pH, these particles adopt a core-shell morphology, with a shell rich in neutralized oligomers. After film formation, the oligomer shell retarded polymer diffusion. This retardation is expected to expand the time window during which the paint surface can be altered without leaving brush marks (open time). Short open time is a pressing problem in current technology.
83

Film Formation of Water-borne Polymer Dispersion: Designed Polymer Diffusion for High Performance Low VOC Emission Coatings

Soleimani Kheibari, Mohsen 31 August 2012 (has links)
In this thesis, I describe experiments that were designed to provide a better understanding of polymer diffusion during latex film formation. This step leads to the improvement of film mechanical properties. Polymer diffusion in these films was monitored by fluorescence resonance energy transfer. Current paint formulations contain Volatile Organic Compounds (VOCs) as plasticizers to facilitate polymer diffusion. The drawback of this technology is the release of VOCs to the atmosphere. VOCs are deleterious to the environment and contribute to smog and ground level ozone formation. The propensity of water, an indispensible part of any latex dispersion, to promote polymer diffusion was studied. Copolymers of poly (butyl acrylate-co-methyl methacrylate) and poly(ethylhexyl acrylate-co-tertiary butyl methacrylate) with similar glass transition temperatures but different hydrophobicity were compared. Polymer diffusion was monitored for films aged at different relative humidities. Water absorbed by the hydrophobic copolymer film was less efficient in promoting polymer diffusion than in the hydrophilic polymer. Only the fraction of water which is molecularly dissolved in the film participate actively in plasticization. Although water has low solubility in most latex polymers, molecularly dissolved water is more efficient than many traditional plasticizers. The possibility of modifying film formation behavior of acrylic dispersions with oligomers was studied by synthesizing hybrid polymer particles consisting of a high molecular weigh (high-M) polymer and an oligomer with the same composition. Oligomers with lower molecular weight are more efficient as diffusion promoters and have less deleterious effect on high-M polymer viscosity. A different set of hybrid particles were prepared in which the oligomer contained methacrylic acid units. The composition of the oligomer was tuned to be miscible with the high-M polymer when the acid groups were protonated but to phase separate when the acid groups were deprotonated. At basic pH, these particles adopt a core-shell morphology, with a shell rich in neutralized oligomers. After film formation, the oligomer shell retarded polymer diffusion. This retardation is expected to expand the time window during which the paint surface can be altered without leaving brush marks (open time). Short open time is a pressing problem in current technology.
84

Texture de la purée de pomme : influence de la structure sur les propriétés rhéologiques et la perception sensorielle - effet du traitement mécanique.

Espinosa Munoz Brisset, Lucia carolina 31 January 2012 (has links) (PDF)
Les purées de fruits sont considérées ici comme des dispersions concentrées de particules végétales déformables et insolubles dans une phase continue aqueuse ou sérum riche en sucre et contenant des pectines solubles. La phase dispersée est constituée de cellules ou d'amas de cellules de parenchyme dont les parois insolubles ne représentent qu'une très faible masse (un peu plus de 1 % p/p) dispersées dans un sérum dont elle sont remplies. La constitution et les propriétés rhéologiques des purées vont dépendre de plusieurs facteurs internes tels que la variété de fruit et l'état de maturité et de facteurs externes tels que les paramètres liées au procédé de transformation (traitement mécanique et thermique). Par ailleurs, la texture est l'un des principaux attributs de qualité des purées et constitue à ce titre une source potentielle importante dans le développement de produits nouveaux. L'objectif général de ce travail a été de mieux comprendre les relations entre les propriétés rhéologiques, structurales et sensorielles des purées de pomme dans la perspective d'identifier des leviers d'action pour le pilotage " à façon " de la texture des produits. La stratégie de recherche a consisté à réaliser l'ensemble de l'étude à partir d'une même lot d'une purée issue d'une seule variété de pomme : Golden Delicious et à identifier les axes majeurs permettant de créer des structures et textures variées. Les trois paramètres structuraux qui ont été modifiés sont : la concentration en parois cellulaires (liée à la quantité de particules de pulpe), la taille des particules et la viscosité de la phase continue. Une technique de séparation - reconstitution couplée à un traitement de broyage ainsi que l'augmentation de la viscosité du sérum ont permis d'obtenir une large gamme de textures et de structures. La construction de deux plans expérimentaux a permis de maîtriser la préparation des produits pour l'étude des relations entre la structure, la rhéologie et la texture des purées. La caractérisation physique et sensorielle a mis en évidence l'importance des paramètres structuraux sur le comportement rhéologique et la perception de la texture des purées. Ainsi la concentration en particules a un effet de premier ordre, suivi par la granulométrie et la viscosité du sérum. L'augmentation de la teneur en particules se traduit directement au niveau de l'état d'encombrement du milieu qui dépend de leur taille. Un traitement mécanique entraîne la séparation des amas des cellules de parenchyme en cellules individualisées, ce changement de structure implique des modifications marquées de propriétés. La caractérisation rhéologique et structurale a permis d'établir des modèles rhéologiques et de mieux comprendre le comportement, l'état et le rôle des particules (molles et déformables) sur la structuration du milieu ainsi que le volume occupé par celles-ci. Cette approche a été complétée et validée par l'observation des dispersions par différentes techniques microscopiques. Les différents régimes de concentration, du régime dilué à l'état d'encombrement et de compaction du régime concentrée des purées ont pu être mis en évidence. Les deux axes principaux qui suffisent à décrire la texture sensorielle d'une purée sont la " consistance " et la " granulosité ". La viscosité de la phase continue a un impact sur la perception de la " granulosité " comme sur la cohésion du réseau particulaire. Les résultats montrent que la texture des dispersions végétales peut être " pilotée " à partir de la maîtrise de quelques grandeurs clés : la concentration en parois cellulaires (pulpe) et la granulométrie des particules complété par la viscosité de la phase continue. De grandes possibilités d'innovation sont ouvertes en jouant sur ces leviers notamment à partir des possibilités offertes au niveau des paramètres du procédé de fabrication.
85

Development of a spray process for manufacturing carbon nanotube films

Dutta, Madhuri January 2015 (has links)
This dissertation describes the development of a processing route for fabricating conventional and doped multi-wall carbon nanotube (MWCNT)/polymer composite films for dielectric applications. Previous research has shown that such composites are promising dielectric materials, but their commercial development has been impeded by the nanotube agglomeration in the polymer matrix and the inefficiency in forming uniform films. Moreover, the harsh fabrication treatments often disrupt the structure of the nanotubes, hence damaging their inherent electrical properties. This work presents safer routes for forming non-aqueous, surfactant free dispersions of conventional and doped MWCNTs, which can be readily mixed with polymers and formed into films through aerosol spraying. Dispersibility behaviour of in-house synthesised conventional, nitrogen doped (N-MWCNTs), and boron doped (B-MWCNTs) MWCNTs was studied in 22 organic solvents. Based on thermodynamic theories it was suggested that doping, in particular nitrogen doping, significantly reduced the surface energy of the nanotubes. This aspect was crucial to understand the dispersibility of N-MWCNTs in low surface energy solvents and to achieve dispersions with high nanotube concentrations (0.82 mg/ml). Also, a "destruction reduced sonication protocol" involving mild sonication was suggested for forming MWCNT dispersions in organic solvents. Dispersions formed using this protocol were homogeneous and showed high stability of at least 2.5 years. Furthermore, the effect of ultrasonic probes on MWCNT lengths was studied and a decrease of 96–99% for MWCNTs and 85–95% for N-MWCNTs was observed. A numerical value for the nanotube length decrease during sonication has been reported for the first time. Preliminary studies to generate dielectric films of MWCNT/perfluoro alkoxy polymer were performed using aerosol spraying. An improvement in the dielectric constant (3.56) with a low dissipation factor (0.003) was observed in 0.3 wt.% B- MWCNT/PFA composite films. Consistency in the test results from various parts of the films confirmed the uniformity of the nanotube distribution within the composite. Future work should concentrate on the effects of B-MWCNTs and N-MWCNTs at the percolation threshold due to their inherent electric properties.
86

Estudo comparativo de metodos de determinacao do tamanho de particula

PAPINI, CLAUDEMIR J. 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:48:55Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:35Z (GMT). No. of bitstreams: 1 09604.pdf: 6894956 bytes, checksum: 537f0618ac453f105325642d96ab808b (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
87

Estudo da influência do teor de segmentos hidrofílicos na síntese de poliuretanos dispersos em água / Study of the influence of the hydrophilic segments content in the synthesis of waterbome polyurethanes

Cristiane Cardoso dos Santos 22 June 2007 (has links)
Considerações ambientais têm aumentado a pesquisa e o desenvolvimento de sistemas poliméricos aquosos para diversos tipos de aplicações, principalmente como revestimentos. Nesta dissertação, foram sintetizadas formulações não-poluentes à base de poliuretanos dispersos em água (PUDs), com 40% de teor de sólidos, na ausência de solventes orgânicos. Os monômeros empregados foram copolímeros em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 25% de segmento hidrofílico EG, poli (glicol propilênico) (PPG), ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e hidrazina (HYD), como extensor de cadeia. Foram variadas as razões entre o número de equivalente-grama de grupamentos isocianato e hidroxila (NCO/OH) e a proporção em equivalente-grama de PPG e dos copolímeros em bloco (EG-b-PG). Foi observado que a incorporação de altas quantidades de copolímero dificultou a síntese dos poliuretanos dispersos em água, levando à formação de géis. O tamanho médio de partícula e a viscosidade das dispersões foram determinados. Os filmes vazados a partir dessas dispersões foram avaliados quanto à capacidade de absorção de água, resistência mecânica, termogravimetria (TG), e caracterizados por espectroscopia na região do infravermelho (FTIR). As dispersões poliuretânicas produzidas se mostraram satisfatórias quando aplicadas como revestimento para madeira, metais e vidro / Environmental considerations are increasing the research and development of waterborne polymeric systems for many different applications, particularly as coatings. In this dissertation, non-polluting formulations based on waterborne polyurethanes (WPU), with 40% solids content, were synthesized in the absence of organic solvents. The monomers (polyols) employed were block copolymers of ethylene glycol and propylene glycol (EG-b-PG), with 25% of EG hydrophilic segments, poly(propylene glycol) (PPG), dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI) and hydrazine (HYD), as chain extender. The ratio between the number of equivalent-grams of isocyanate and hydroxyl groups (NCO/OH) and the ratio between the equivalent-grams of PPG and (EG-b-PG) were varied. It was observed that the incorporation of high quantities of the copolymer resulted in gels instead of dispersions. The average particle size and the viscosity of the resins were determined. Thermal and mechanical resistances and water absorption of cast films produced from the dispersions were evaluated. The chemical structure of the chains was characterized by infrared spectroscopy (FTIR). The waterborne polyurethanes showed to be suitable as coatings for wood, metals and glass
88

Estudo da incorporação de diferentes tipos de argilas hidrofílicas em dispersões aquosas de poliuretanos para formação de nanocompósitos / Study of incorporation of different hydrophilic clays in nanocomposites of water born polyurethanes

Gisele dos Santos Miranda 15 July 2009 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho foram sintetizados nanocompósitos à base de poliuretanos em dispersão aquosa (NWPUs) e argilas hidrofílicas do tipo montimorilonita (MMT) de natureza sódica e cálcica. Os monômeros empregados na síntese foram: poli(glicol propilênico) (PPG); copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 7% de EG; ácido dimetilolpropiônico (DMPA) e diisocianato de isoforona (IPDI). Os NWPUs tiveram as argilas, previamente deslaminadas em água e incorporadas à formulação no momento da dispersão do prepolímero. Dispersões aquosas (WPUs), sem a presença de argila, foram sintetizadas como base, nas quais foram variadas a razão NCO/OH e a proporção de copolímero em relação ao PPG. Nas formulações NWPUs, foram variados também o teor de argila em relação à massa de prepolímero e o tipo de argila sódica e cálcica. As dispersões foram avaliadas, quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade. Os filmes vazados a partir das dispersões foram caracterizados por espectrometria na região do infravermelho (FTIR), difração de raios-x (XRD) e microscopia eletrônica de varredura (SEM). A resistência térmica dos filmes foi determinada por termogravimetria (TG) e a resistência mecânica dos filmes foi avaliada por ensaios mecânicos em dinamômetro. O grau de absorção de água dos filmes também foi determinado. A formação de nanocompósitos à base de água foi confirmada pela ausência do pico de XRD, característico das argilas empregadas na maioria dos filmes analisados. As micrografias obtidas por SEM confirmam uma dispersão homogênea das argilas na matriz poliuretânica. Os filmes à base de nanocompósitos (NWPUs) apresentaram propriedades superiores às apresentadas por aqueles obtidos a partir das dispersões sem argilas (WPUs). Os revestimentos formados a partir da aplicação das dispersões aderiram à maioria dos substratos testados (metal, vidro, madeira e papel) formando superfícies homogêneas / In this work nanocomposites (NWPUs) based on waterborne polyurethanes and hydrophilic montimorillonite clays (MMT) were synthesized. Polypropyleneglycol (PPG), poly(ethylene glycol-b-propylene glycol) (EG-b-PG) containing 7% of ethylene glycol (EG), dimethylolpropionic acid (DMPA) and isophorone diisocyanate (IPDI) were employed in polyurethane synthesis. The NWPUs were prepared with calys previously exfoliated in water, and were added at the moment of dispersion. Different formulations were obtained from WPUs, without clays, by varying the NCO/OH ratio, and the proportions of PPG and EG-b-PG. For NWPUs formation was varied the content of clays with different cations (Na+ and Ca+2). The properties of the dispersions were evaluated in terms of their solid content, particle size and viscosity. The cast films obtained were characterized by infrared spectrometry (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM). The thermal stability of the films was evaluated by thermogravimetry (TG) and mechanical properties in a dynamometry. X-ray diffraction and scanning electron microscopy examinations were determined confirming the nanocomposite formation. NWPUs films showed improved properties in comparison with WPUs Coatings obtained by the application of the dispersions in substrates as wood, metals, paper and glass were homogeneous and showed good adherence
89

Síntese e caracterização de nanocompósitos à base de poliuretano dispersos em água com argilas hidrofílica e organofílica / Synthesis and characterization of nanocomposites based on polyurethanes dispersed in water with hydrophilic and organophilic clays

Claudia Pacheco Garcia 05 July 2010 (has links)
A área de pesquisa de materiais nanoestruturados tem recebido destacada atenção nos últimos anos por parte da comunidade científica, ressaltando-se os nanocompósitos à base de polímero e argila. Nesta Dissertação foram sintetizados nanocompósitos à base de poliuretano (NWPUs) com argilas do tipo montmorilonita (MMT), hidrofóbicas (organofílicas) e hidrofílica. Os monômeros empregados na síntese foram poli(glicol propilênico) (PPG); polibutadieno líquido hidroxilado (HTPB); ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e hidrazina (HYD), como extensor de cadeia. Nas formulações, foram variadas as proporções de HTPB e o teor das argilas. As argilas organofílica Cloisite 30B e hidrofílica Cloisite Na+ foram incorporadas em 1, 3 e 5 %, enquanto que a organofílica Cloisite 15A foi incorporada no teor de 1%. As dispersões foram caracterizadas quanto ao teor de sólidos totais, tamanho médio de partículas e viscosidade. Os filmes vazados a partir das dispersões foram caracterizados por espectroscopia na região do infravermelho (FTIR), difração de raios-x (XDR), microscopia eletrônica de varredura (SEM) e microscopia de força atômica (AFM). A resistência térmica e a transição vítrea dos materiais foram determinadas por termogravimetria (TG) e calorimetria diferencial de varredura (DSC), respectivamente. O teor de absorção de água e o comportamento mecânico dos filmes foram avaliados. Foi verificada, por XRD, a ausência do pico de cristalinidade, característico das argilas puras e não-deslaminadas. As micrografias obtidas por SEM confirmam uma dispersão homogênea das argilas na matriz poliuretânica. Os filmes à base de nanocompósitos (NWPUs) apresentaram propriedades mecânicas superiores às apresentadas por aqueles obtidos a partir das dispersões sem a presença de argila (WPUs). A adesão dos revestimentos formados, pela aplicação das dispersões em diversos substratos, também foi verificada visualmente. Os resultados das análises mostraram que houve a formação de nanocompósitos à base de água, formados tanto a partir da argila hidrofílica quanto das organofílicas
90

Caracterização estrutural de dispersões aquosas de lipídios aniônicos / Structural characterization of aqueous dispersions of anionic lipids

Daniela Akiko Nomura 10 April 2018 (has links)
É conhecido que a força iônica do meio desempenha um papel fundamental na estrutura de vesículas aniônicas de DMPG (dimiristoil fosfatidilglicerol) em dispersões aquosas. A baixa força iônica (~ 6 mM), as dispersões de DMPG exibem várias características anômalas, que foram interpretadas como a abertura de poros na bicamada ao longo da larga região de transição de fase gel-fluida (de ~ 18°C a 30°C). Aqui, revisitamos o sistema de DMPG em tampão a baixa força iônica, mas com dispersões obtidas após a extrusão por filtros de 100 nm, portanto menos polidispersas. Para enfatizar as interações eletrostáticas entre as cabeças polares dos lipídios, que não estarão blindadas pela presença de sais na solução, estudamos dispersões de DMPG em água pura, de modo a monitorar os agregados presentes na dispersão, e suas interações. As dispersões em água foram caracterizadas antes e depois da extrusão. Para tal, utilizamos diversas técnicas experimentais, em diferentes temperaturas: espalhamento de luz estático (SLS) e dinâmico (DLS), calorimetria diferencial de varredura (DSC), Ressonância Paramagnética Eletrônica (RPE) de marcadores de spin incorporados aos agregados, espalhamento de raios-X a altos e baixos ângulos (WAXS e SAXS), e medidas de viscosidade, turbidez, mobilidade eletroforética e condutividade elétrica. Resultados das várias técnicas com dispersões extrusadas de DMPG em tampão mostraram que o comportamento anômalo é observado de forma similar ao de dispersões não extrusadas. Entretanto, o pico de SAXS em muito baixo ângulo é visto de 5 a 45°C, e não apenas na região de transição de fase, portanto não deve ser modelado como a distância entre poros na bicamada lipídica que se abririam nesta região. A distância de repetição relacionada a este pico diminui na região de transição de fase, e com o aumento da concentração lipídica. Medidas de DSC indicaram que, em água, a região de transição de fase da vesícula de DMPG é ainda mais ampla, começando em torno de 10°C, mas ainda terminando em ~ 30oC. No entanto, a alta condutividade elétrica, viscosidade, mobilidade eletroforética, raio efetivo, e a baixa turbidez, vistas apenas na região de transição de fase do DMPG em tampão, são encontradas até altas temperaturas em água, quando a bicamada lipídica já se encontra na fase fluida. Medidas de RPE e WAXS mostraram a transição da membrana de uma fase mais rígida/imóvel/organizada para uma fase mais frouxa/móvel. Dados de espalhamento de luz, RPE e SAXS mostram que, similar ao DMPG em tampão, em água, o DMPG organiza-se como vesículas esféricas, unilamelares, mas possivelmente menores e mais carregadas, exibindo fortes interações vesícula-vesícula. Nas medidas de SAXS, o pico de Bragg na região de muito baixo ângulo foi visto em todas as temperaturas (de 5 a 60°C), sendo que a distância de repetição diminui para temperaturas maiores do que 10oC. Os resultados obtidos para dispersões em água, reforçam o comportamento anômalo observado anteriormente para dispersões em tampão em baixa força iônica. De acordo com eles, propomos a existência de vesículas altamente deformadas e ionizadas a partir de uma certa temperatura, T1 para o DMPG em água e Tmon em tampão baixa força iônica, sendo que em água a forte repulsão eletrostática PG--PG- levaria a fortes deformações e interações vesícula-vesícula, em uma ampla extensão de temperaturas. / It is known that the ionic strength plays a fundamental role in the structure of DMPG (dimyristoyl phosphatidylglycerol) anionic vesicles in water medium. At low ionic strength (~ 6 mM), DMPG dispersions display several anomalous characteristics, which were interpreted as the opening of bilayer pores along the wide bilayer gel-fluid transition region (from ~ 18°C to 30°C). Here, we revisit DMPG in buffer at low ionic strength, but with dispersions obtained after the extrusion by 100 nm filters, thus less polydisperse. To emphasize electrostatic interactions between the polar head-groups, which will not be shielded by ions in solution, we studied DMPG dispersions in pure water to monitor the aggregates in the dispersion and their interactions. Water dispersions were characterized before and after extrusion. For such, we used several experimental techniques, at different temperatures: light scattering, both static (SLS) and dynamic (DLS); differential scanning calorimetry (DSC); electron spin resonance (ESR) of spin labels incorporated into the aggregates, Small and Wide Angle X-Ray Scattering (SAXS and WAXS); and viscosity, turbidity, electrophoretic mobility and electrical conductivity measurements. Several techniques with extruded dispersions of DMPG in buffer showed that the anomalous behavior is also observed. However, the SAXS peak at very low angles is seen from 5 to 45°C, and not only in the phase transition region, therefore it should not be modeled as the distance of correlated pores in the lipid bilayer that would open in this region. The repeating distance related to this peak decreases in the phase transition region, and with increasing lipid concentration. DSC indicates that, in water, the bilayer gel-fluid transition is even wider, starting around 10oC but still ending ~ 30oC. However, high electric conductivity, viscosity, electrophoretic mobility, effective radius and low turbidity found only in the gel-fluid transition region for DMPG in buffer, are found at higher temperatures in water, when lipid bilayers are already in the fluid state. ESR and WAXS measurements evidenced the transition of the membrane from a more rigid/immobile/organized phase to a more soft/mobile phase. Light scattering, ESR and SAXS data showed that, similar to DMPG in buffer, in water, DMPG is organized as spherical unillamelar vesicles, but possibly smaller, highly charged, displaying strong vesicle-vesicle interactions. With SAXS the Bragg peak at very low angles was seen at all temperatures (from 5 to 60°C) with the repetition distance decreasing at temperatures higher than 10 ° C. The results obtained for water dispersions reinforce the anomalous behavior previously observed for buffer at low ionic strength dispersions. According to them, we propose the existence of highly deformed and ionized vesicles from a certain temperature, T1 for DMPG in water and Tmon in buffer at low ionic strength. In water the strong PG- - PG- electrostatic repulsion would lead to strong deformations and vesicle-vesicle interactions, over a wide range of temperatures.

Page generated in 0.0875 seconds