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Master's Dissertation
DOI
https://doi.org/10.11606/D.46.1982.tde-27052011-165916
Document
Author
Full name
Maria Regina Alcantara
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 1982
Supervisor
Title in Portuguese
Rmn de 2H, texturas e disclinações em liomesofases colestéricas induzidas e intrínsecas
Keywords in Portuguese
Colestéricos
Cristais líquidos
Liomesofases
Ressonância magnética nuclear
Abstract in Portuguese
Na presente dissertação investigou-se sistemas colestéricos liotrópicos induzidos e intrínsecos. Colestéricos induzidos por adição de pequenas quantidades de colesterol, em liomesofases à base de Laurato de Potássio (LK), foram estudados por RMN de 2H e microscopia óptica sob luz polarizada. A comparação dos perfis de ordem obtidos para liomesofases colestéricas induzidas, através de RMN de 2H de cadeias perdeuteradas de LK, com aqueles correspondentes a mesofases normais, mostrou a ausência de grandes distorções micelares, o que indica que o principal responsável pela colestericidade do sistema deve ser uma distribuição assimétrica de carga na superficie micelar. As amostras colestéricas induzidas tipo II apresentaram o padrão "chevron" esperado ao microscópio polarizado, após serem submetidas à ação de H paralelo à superfície do capilar de paredes paralelas. Quando a estas liomesofases aplicou-se um campo Ho normal ao plano da cela, observou-se uma textura focal-cônica. Os padrões obtidos ao microscópio polarizado para as liomesofases colestéricas induzidas tipo I, submetidas à campo magnético, mostraram a existência de dois tempos de orientação. O primeiro devido ao alinhamento da hélice perpendicular a Ho e o segundo devido ao desenrolamento da superestrutura helicoidal. As liomesofases colestéricas intrínsecas se basearam no anfifílico N-Lauroil-Serinato de Potássio (NLSK) na forma levo. Este foi obtido pela acilação do amino-ácido correspondente, havendo retenção de configuração pelo produto. Todas mesofases obtidas foram caracterizadas por RMN de 2H da HDO e Microscopia Óptica. Estudos de microscopia sob luz polarizada, desenvolvidos em fases colestéricas intrínsecas do tipo I, expostas a campos magnéticos, corroboraram a hipótese de dois tempos de orientação estabelecido para as fases colestéricas induzidas, caracterizando definitivamente o sistema como colestérico. A caracterização de liomesofases colestéricas intrínsecas do tipo II foi feita por técnicas de RMN de 2H. Estas mesofases, após orientadas em campo magnético, apresentaram uma nova textura colestérica ao microscópico polarizado, diferente do padrão chevron esperado. Esta nova textura pode ser explicada pelas teorias de disclinações desenvolvidas para cristais líquidos termotrópicos, em especial para os colestéricos. Adicionalmente, verificou-se que a forma racêmica do anfifílico (d,1-NLSK) conduziu a mesofases "nemáticas".
Title in English
Deuterim NMR, textures and disclinations on induced, intrinsic cholesteric lyomesophases
Keywords in English
Cholesterics
Liquid crystals
Lyomesophases
Abstract in English
Induced and intrinsic cholesteric lyotropic mesophases were studied in the present dissertation. Induced cholesteric lyomesophases based on potassium laurate (KL) system, with small amounts of cholesterol added, were studied by deuterium NMR and by polarizing microscopy. Order profiles obtained from deuterium NMR of KL perdeuterated chains in both induced cholesteric and normal mesophases were compared. The similarity of the profiles indicates that great distortions in micelles should not be present and an interaction between micelles with assyrnetric distribution of charges in their surfaces be responsible for the cholestericity of the system. The induced cholesteric type II samples presented the usual "chevron" pattern, when observed at the polarizing microscope after exposition to a magnetic field parallel to the capillar cell surface. When a field normal to the cell was applied a focal-conic texture was observed. For type I induced cholesteric mesophases, the patterns observed at the polarizing microscope indicated the existence of two orientational times in the magnetic field. The first is due to the alignment of the helix perpendicularly to the field and the second to the untwisting of the helicoidal structure. The intrinsic cholesteric lyotropic mesophases were based on the amphiphile potassium N-lauroyl-serinate (KNLS) in the resolved levo form. This compound was synthesized by acilation of the correspondent resolved amino-acid, with retention of configuration. All of obtained mesophases were characterized by deuterium NMR of the HDO and by optical microscopy under polarized light. The study of the type I intrinsic cholesteric mesophase at the polarizing microscope corroborated the hypothesis of two orientational times in magnetic field above mentioned for the induced cholesteric phases, and characterized the cholestericity of this system. Type II intrinsic cholesteric lyomesophase was characterized by deuterium NMR. Oriented samples of this mesophase when observed at the polarizing microscope showed a new cholesteric texture, different from the usual chevron pattern. The new texture was explained by the use of the theory of disclinations developed for thermotropic liquid crystals, specially for cholesteric type. Additionaly, it was verified that the racemic form of the amphiphile (d,l-KNLS) yielded "nematic" mesophases.
 
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Publishing Date
2011-05-27
 
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