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Doctoral Thesis
DOI
https://doi.org/10.11606/T.46.2016.tde-05022016-091807
Document
Author
Full name
Idélcio Nogueira da Silva
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2002
Supervisor
Committee
Politi, Mario Jose (President)
Feitosa, Eloi da Silva
Itri, Rosangela
Kawano, Yoshio
Paula, Eneida de
Schreier, Shirley
Title in Portuguese
Caracterização de agregados supramoleculares: interação de vesículas de Doda com polimetacrilato (OU) Caracterização de agregados supramoleculares: interação de vesículas de dioctadecildimetilamônio com polimetacrilato
Keywords in Portuguese
Conformação de polímeros
Estabilidade de vesículas
Físico-química orgânica
Fluorescência
Interação polímero-vesícula
Macromolécula (Estudo)
Polimerizaçao
Polímeros (Química orgânica)
Química de superfície
Abstract in Portuguese
Este trabalho teve como objetivo estudar a interação de polimetacrilato com vesículas de metacrilato de dioctadecildimetílamônio (DODAM) e brometo de dioctadecildimetilamônio (DODAB). A fotoirradiação de vesículas de DODAM a formou polimetacrilato na superfície vesicular do polímero, através da polimerização do contra-íon. Vesículas polimerizadas foram mais estáveis frenta á adição de metanol do que vesículas não polimerizadas. A estabilização da bicamada vesicular foi confirmada com o aumento da retenção da carboxifluoresceína (CF). Vesículas injetadas de DODAM retiveram cerca de 25% de CF, enquanto que vesículas polimerizadas retiveram cerca de 75%. Experimentos de temperatura de transição de fase por turbidez e tensão superfícial mostraram que o polimetacrilato formado na superfície vesicular diminui a temperatura de transição de fase e reduz a cooperatividade. A interação de fosfatase alcalina (Fal) com vesículas de DODAM e colinametacrilato de dicetilfosfato (DCM) foi estudada, como um primeiro passo para a construção de um micro-reator. Foi observada a precipitação na presença de DODAM, mas não em presença de DCM. Isto pode ser explicado pela forte interação entre a superfície de vesículas de dioctadecildimetilamônio (bicamada com carga negativa) com a fosfatase alcalina (carga negativa). Esta precipitação não foi observada com vesículas de DCM (bicamada negativa). Experimentos de monocamada confirmaram estes resultados. DCM e DODAM formaram monocamadas mistas estáveis, sugerindo que vesículas mistas poderiam ser usadas para superar as interações eletrostáticas fortes entre os surfactantes e a enzima.
Title in English
Characterisation of supramolecular aggregates: interaction of dioctadecyldimethylammonium vesicles with polymethacrylate
Keywords in English
Conformation of polymers
Fluorescence
Interaction polymer-bladder
Macromolecule (Study)
Organic physical chemistry
Polymerization
Polymers (Organic Chemistry)
Surface chemistry
Vesicles stability
Abstract in English
This work had as objective studying the interaction of polymethacrylate with dioctadecyldimethylammonium methacrylate (DODAM) and brornide (DODAB). The fotoirradiation of vesicular suspensions of DODAM formed polymethacrylate on the vesicle surface though counter-ion polymerization. Polymerized vesicles were more stables on methanol addition than non-polymerized vesicles. Bilayer stability was confirmed with the retention of carboxyfluorescein (CF). DODAM injected vesicles without polymerization retained about 25% of CF, while polymerized DODAM retained about 75%. Experiments of phase transition temperature by turbidity and surface tension showed that polymethacrylate formed at vesicle surface drops phase transition temperature and reduces cooperativity. Polymethacrylic acid and polymethacrylic acid containing rodhamine B covalently linked was used to monitor polymer-vesicle interaction. Experiments showed that the polymer interacts electrostatically with the DODAB bilayer, causing precipitation and or aggregation. The polymer, initially on a confonnation with many hipercoiled hydrophobic regions, opens as interacts with DODAB vesicles. The interaction of alkaline phosphatase (Fal) with vesicles of DODAM and colina-methacrylate dicetylphosphate (DCM) was studied, as a preliminary step for a micro-reactor construction. Precipitation was observed in presence of DODAM, but not in presence of DCM. This may be explained by the strong interaction between the surface of dioctadecyldimethy lammonium vesicles (positive charged bylayer) with Fal (negative charge). This precipitation was not observed with DCM vesicles (negative charged bilayer). Monolayer experiments confirm these results. Experiments showed that DCM and DODAM form stabled mixed monolayers. Suggesting that mixed vesicles could be tried to overcome strong electrostatic interactions between surfactants and enzyme.
 
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Publishing Date
2016-02-05
 
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