RESUMO
In this communication, we describe for the first time the integration of concentric electrodes (wrapping around the microchannel) in microchips. The use of such electrodes has been shown to be effective towards improvement of the sensitivity and detectability in pressure-driven flow platforms incorporating C(4)D.
Assuntos
Técnicas Eletroquímicas/instrumentação , Análise de Injeção de Fluxo , Dimetilpolisiloxanos/química , Condutividade Elétrica , Eletrodos , Pressão , Dióxido de Silício/químicaRESUMO
This manuscript describes results related to the characterization of electrodes modified with a composite of acetylcholinesterase covalently bound to carbon nanotubes (CNT). The characterization was performed by computational methods and complemented by cyclic voltammetry, infrared spectroscopy, and electrochemical impedance spectroscopy. In-silico simulations enabled the identification of the binding site and the calculation of the interaction energy. Besides complementing the computational studies, experimental results obtained by cyclic voltammetry showed that the addition of CNT to the surface of electrodes yielded significant increases in effective area and greatly facilitated the electron transfer reactions. These results are also in agreement with impedance spectroscopy data, which indicated a high apparent rate constant, even after the immobilization of the enzyme. These results lend new information about the physical and chemical properties of biointerfaces at the molecular level, specifically about the mechanism and consequences of the interaction of a model enzyme with CNT.
Assuntos
Acetilcolinesterase/metabolismo , Simulação por Computador , Eletroquímica/métodos , Electrophorus/metabolismo , Nanotubos de Carbono/química , Acetilcolinesterase/química , Animais , Sítios de Ligação , Espectroscopia Dielétrica , Ligação Proteica , Estrutura Secundária de Proteína , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The problem of non-stationarity in experimentally recorded time-series is common in many (electro)chemical systems. Underlying this non-stationarity is the slow drift in some uncontrollable parameter, and it occurs in spite of the fact that all controllable parameters are kept constant. Particularly for electrochemical systems, some of us have recently suggested [J. Phys. Chem. C, 144, (2010), 22262-22268] an empirical method to stabilize experimental time-series. The method was exemplified for the electro-oxidation of methanol and different patterns were satisfactorily stabilized. In this paper we further elaborate some mechanistic aspects of this method and test it for the electro-oxidation of formaldehyde, a system that has some resemblance with the electro-oxidation of methanol, but produces a richer dynamics. In terms of the reaction mechanism, we were able to describe the coupling and to separate the surface processes of the two sub-systems: the fast one (or the core-oscillator) and the slow one, responsible for the drift.
RESUMO
Monolayers of 3,3'-dithiodipropionic acid (DTDPA) were prepared on a polycrystalline gold electrode through a self-assembly procedure to produce a gold 3,3'-dithiodipropionic acid self-assembled monolayer (AuDTDPA) modified electrode. The characterization of the AuDTDPA electrode was investigated by cyclic voltammetry and ac impedance using the [Fe(CN)(6)](3-/4-) redox couple. The electrochemical behavior of DA on the modified electrode AuDTDPA was studied by cyclic and square-wave voltammetries, using phosphate buffer as supporting electrolyte. The oxidation peak current for DA increases linearly with concentration in the range of 0.35x10(-5) to 3.4x10(-5)molL(-1). The performance of the AuDTDPA modified electrode was evaluated for the electroanalytical determination of dopamine (DA) in a pharmaceutical formulation. The AuDTDPA modified electrode showed a stable behavior and the presence of surface-COOH groups avoided the passivation of the electrode surface during the dopamine oxidation.