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Doctoral Thesis
DOI
https://doi.org/10.11606/T.46.2013.tde-15012014-151210
Document
Author
Full name
Fernando Castro Mota de Oliveira
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2013
Supervisor
Committee
Serrano, Silvia Helena Pires (President)
Angnes, Lucio
Faria, Ronaldo Censi
Ferreira, Tiago Luiz
Paixão, Thiago Regis Longo Cesar da
Title in Portuguese
Mecanismos redox e aplicações analíticas de L-Cisteína e L-Glutationa ancoradas sobre eletrodos de ouro recobertos com camadas auto-arranjadas de ácido 3-mercaptopropiônico
Keywords in Portuguese
Antioxidantes
Camadas auto- arranjadas
Espécies reativas de oxigênio
L-cisteína
L-glutationa
Ponte de dissulfeto
Voltametria cíclica
Abstract in Portuguese
Moléculas de L-cisteína (CSH) e L-glutationa (GSH) foram ancoradas na superfície de eletrodos de ouro, previamente modificados com uma camada autoarranjada de ácido 3-mercaptopropiônico (MPA). Esta arquitetura molecular foi importante para preservar a atividade redox dos grupos tiólicos da CSH e GSH na interface eletrodo/solução. A identificação do par redox R-S-S-R/R-SH, bem como a determinação do pKa dos grupos -SH superficiais, foram efetuadas usando voltametria cíclica em soluções de eletrólito em diferentes pH contedo ferricianeto de potássio. A presença dos grupos -SH e -S-S- na superfície dos eletrodos modificados foi ainda confirmada por Espectroscopia Raman de Superfície. Determinaram-se as constantes de velocidade de transferência de carga do processo quase reversível R-S-S-R / R-SH. Estes eletrodos modificados apresentaram resposta eletrocatalítica para a redução de espécies reativas de oxigênio (ROS), como peróxido de hidrogênio e para a oxidação de compostos com atividade antioxidante como a quercetina. Demonstrou-se que a presença de íons Cu2+ na superfície destes eletrodos é capaz de deslocar o equilíbrio do par R-SS-R/R-SH, no sentido oxidativo. Métodos de quantificação para estes compostos foram desenvolvidos por amperometria hidrodinâmica e voltametria cíclica.
Title in English
Redox mechanism and analytical applications of L-cysteine and L-Glutathione binded over gold electrodes modified with 3-mercaptopropionic acid self assembled monolayer
Keywords in English
Antioxidants
Cyclic voltammetry
Disulfide bridge
L-cysteine
L-glutathione
Reactive oxygen species
Self assembled mono layers
Abstract in English
L-cysteine molecules (CSH) and L-glutathione (GSH) were anchored on the surface of gold electrodes, previously modified with a self assembled monolayer of 3-mercaptopropionic acid (MPA). This molecular architecture was important to preserve the redox properties of the thiol groups of CSH and GSH in the interface electrode / solution. The identification of the redox couple RSSR / R-SH and the determination of the pKa of -SH groups surface were made using cyclic voltammetry in electrolyte solutions at different pH contents potassium ferricyanide. The presence of the -SH and -SS- modified electrode surface was further confirmed by Raman spectroscopy of surface. It was determined the rate constants of direct electron transfer of quasi-reversible coupled R-SS-R/R-SH. The modified electrodes showed electrocatalytic response to the reduction of reactive oxygen species (ROS) such as hydrogen peroxide and the oxidation of compounds with antioxidant activity such as quercetin. It was demonstrated that presence of Cu2+ ions on the electrode surface can shift the equilibrium of the RSSR/R-SH redox coupled into oxidative direction. Hydrogen peroxide and Quercetin were detected at these modified electrodes using amperometry and hydrodynamic cyclic voltammetry.
 
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Publishing Date
2014-03-18
 
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