Interactions of valproic acid with lipid membranes of 1,2-dimyristoyl-sn-glycero-3-phosphocholine.

Lipid bilayers of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) were prepared in two forms, as a suspension of multilamellar spherical vesicles and as planar membranes deposited on a conductive solid support. We used Fourier Transformed Infrared (FTIR) and Raman spectroscopic techniques to study the lipid vesicles while the solid supported bilayers were characterized by using electrochemical experiments (cyclic voltammetry and impedance). Valproic acid (Valp) was either present in the solution or incorporated into the lipid structure. As the Valp:DMPC ratio increases the phase transition temperature decreases while the phase transition becomes less marked. Moreover, for the Valp:DMPC complex species a slight decrease in the number of gauche isomers was observed relative to the number of trans isomers what corresponds to an increase in the packing density of the acylic chains. Based on derived electrical properties of the supported membranes it can be concluded that Valp induces the formation of pores and other defects in the lipid films. Valp incorporated into the membrane is seriously detrimental to the bilayer stability.

Estimating diffusion coefficients of probe molecules into polyelectrolyte brushes by electrochemical impedance spectroscopy.

Molecular transport through thin polymer films has become a subject with a variety of challenges and opportunities for chemists, physicists, and material scientists in recent years. The diffusion of probe molecules in and out of macromolecular environments plays a major role in the response of polymer-based sensor materials or the design of time-released drug delivery systems. Obtaining an improved understanding of the relevant dynamic phenomena, like transport of molecular probes, in boundary layers represents a crucial step to develop a clearer picture of the molecular transport processes taking place at interfaces modified with macromolecular assemblies. In this work, we present a new approach based on the derivation of the theoretical impedance transfer function to unambiguously describe the impedance response of gold electrodes modified with poly(methacryloyloxy)-ethyl-trimethyl-ammonium chloride (PMETAC) brushes. We demonstrate that this methodology not only enables the description of the experimental data but also provides insightful information about the dynamics of the diffusion of probe molecules inside the brush. More important, we show the capabilities of electrochemical impedance spectroscopy to gather information on a molecular transport process inside the brush under experimental conditions in which other electrochemical techniques are no longer applicable. As such, we consider that this experimental approach constitutes a new and powerful tool to estimate diffusion coefficients of probe molecules into interfacial macromolecular assemblies.

Impedance analysis of ion transport through supported lipid membranes doped with ionophores: a new kinetic approach.

Kinetics of facilitated ion transport through planar bilayer membranes are normally analyzed by electrical conductance methods. The additional use of electrical relaxation techniques, such as voltage jump, is necessary to evaluate individual rate constants. Although electrochemical impedance spectroscopy is recognized as the most powerful of the available electric relaxation techniques, it has rarely been used in connection with these kinetic studies. According to the new approach presented in this work, three steps were followed. First, a kinetic model was proposed that has the distinct quality of being general, i.e., it properly describes both carrier and channel mechanisms of ion transport. Second, the state equations for steady-state and for impedance experiments were derived, exhibiting the input-output representation pertaining to the model's structure. With the application of a method based on the similarity transformation approach, it was possible to check that the proposed mechanism is distinguishable, i.e., no other model with a different structure exhibits the same input-output behavior for any input as the original. Additionally, the method allowed us to check whether the proposed model is globally identifiable (i.e., whether there is a single set of fit parameters for the model) when analyzed in terms of its impedance response. Thus, our model does not represent a theoretical interpretation of the experimental impedance but rather constitutes the prerequisite to select this type of experiment in order to obtain optimal kinetic identification of the system. Finally, impedance measurements were performed and the results were fitted to the proposed theoretical model in order to obtain the kinetic parameters of the system. The successful application of this approach is exemplified with results obtained for valinomycin-K(+) in lipid bilayers supported onto gold substrates, i.e., an arrangement capable of emulating biological membranes.

Impedance analysis of ion transport through gramicidin channels in supported lipid bilayers.

Selectivity between monovalent cations and its sequence of conductivity in lipid bilayers doped with the antibiotic Gramicidin D (GD) were examined using EIS. Experiments were performed using lipid bilayers obtained from a lipid mixture of phosphatidylcholine and dimethyldioctadecylammonium chloride (DODAC). Lipid bilayers were supported on gold surfaces modified with a mercapto-carboxylic acid. The bilayers were formed by chemisorption of this last species to form the first monolayer on gold and subsequent fusion of unilamellar vesicles to form an external bilayer attached by electrostatic interactions. A mathematical expression for the impedance of the membrane processes was derived. Some predictions of the presented model were checked after fitting the experimental results in various electrolyte compositions.