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Gerardo Prieto

Publications and source records attributed to Gerardo Prieto.

16 recordsLinked to original sources
PubMed2006

Effect of Gd3+ on the colloidal stability of liposomes.

Lanthanide ions such as La3+ and Gd3+ are well known to have large effects on the structure of phospholipid membranes. Unilamellar vesicles of dipalmitoylphosphatidylcholine (DPPC) were prepared by sonication method and confirmed by transmission electron microscopy. The effects of concentration of gadolinium ions Gd3+ on DPPC unilamellar vesicles in aqueous media were studied by different techniques. As physical techniques, photon correlation spectroscopy, electrophoretic mobility, and differential scanning calorimetry were used. The theoretical predictions of the colloidal stability of liposomes were followed using the Derjaguin-Landau-Verwey-Overbeek theory. Changes in the size of liposomes and high polydispersities values were observed as Gd3+ concentration increases, suggesting that this cation induces the aggregation of vesicles. Electrophoretic mobility measurements on unilamellar vesicles as a function of Gd3+ ion concentration show that the vesicles adsorb Gd3+ ions. Above Gd3+ concentrations of 0.1 mol dm-3, the zeta potential and light scattering measurements indicate the beginning of aggregation process. For comparison with similar phospholipids, the zeta potential of phosphatidylcholine interacting with Gd3+ was measured, showing an analogous behavior. Differential scanning calorimetry has been used to determine the effect of Gd3+ on the transition temperature (Tc) and on the enthalpy (DeltaHc) associated with the process.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2006

Surface characterization of human serum albumin and sodium perfluorooctanoate mixed solutions by pendant drop tensiometry and circular dichroism.

The interfacial behavior of mixed human serum albumin (HSA)/sodium perfluorooctanoate (C8FONa) solutions is examined by using two experimental techniques, pendant drop tensiometry and circular dichroism spectroscopy. Through the analysis of the surface tension of the mixed solutions, surface competitive adsorption at the air-water interface between C8FONa and HSA is detected. The dynamic adsorption curves exhibit the distinct regimes in their time-dependent surface tension. The nature of these regimes is further analyzed in terms of the variation of the molecules surface areas. As a consequence, a compact and dense structure was formed where protein molecules were interconnected and overlapped. Thus, a reduction of the area occupied per molecule from 100 to 0.2 nm(2) is interpreted as a gel-like structure at the surface. The presence of the surfactant seems to favor the formation of this interfacial structure. Finally, measurements of circular dichroism suggests a compaction of the protein due to the association with the surfactant given by an increase of alpha-helix structure in the complexes as compared to that of pure protein.

Adsorption↗
PubMed2006

Regarding the effect that different hydrocarbon/fluorocarbon surfactant mixtures have on their complexation with HSA.

The complexations between human serum albumin (HSA) and the sodium perfluorooctanoate/sodium octanoate and sodium perfluorooctanoate/sodium dodecanoate systems have been studied by a combination of electrical conductivity, ion-selective electrode, electrophoresis, and spectroscopy measurements. The binary mixtures of the surfactants deviated slightly from ideality. Binding plots revealed the existence of two specific binding sites, the first site being more accessible than the second. Positive cooperative binding has been found, thus revealing the importance of the hydrophobic interactions in both kinds of surfactants. The Gibbs energies of binding per mole of surfactant (DeltaG(nu)) were calculated from the Wyman binding potential where, on the basis of the elevated number of binding sites, a statistical contribution has been included. Initially these energies are large and negative, gradually decreasing as saturation is approached. Changes in the slope of Gibbs energies have been identified with the saturation of the first binding set. These facts denote that the surfactants under study have different favorite adsorption sites along the protein and that the adsorption process of perfluorooctanoate is more closely followed by dodecanoate than by octanoate. Finally, electrophoresis and spectroscopy measurements suggest induced conformational changes on HSA depending on the surfactant mixture as well as the mixed ratio.

Electric Conductivity↗
PubMed2006

Characterization of phospholipid+semifluorinated alkane vesicle system.

The aim of this study is to characterize vesicles obtained by the incorporation of the semifluorinated alkane, (perfluoro-n-hexyl)ethane (diblock F6H2) to a standard lipid, egg yolk phosphatidylcholine (PC). Large unilamellar vesicles (LUVs), prepared by extrusion, were characterized by fluorescence spectroscopy, zeta potential (zeta-potential) and light scattering. By using the fluorescence spectroscopy technique, the anisotropy of l,6-diphenyl-l,3,5-hexatriene (DPH) probe at different temperatures was determined. It was demonstrated that F6H2 is placed inside of the lipid bilayer and that the hydrocarbon acyl chain in the bilayers has higher viscosity in the presence of fluoroalkane. The zeta-potential of the PC-F6H2 system is negative and increases (in absolute value) from -10 to -19 mV when the temperature rises from 10 to 25 degrees C, this last value keeping practically constant with a further increase of temperature. The adsorption of K+ ions on the liposome surface was measured by zeta-potential. This adsorption originates a sudden increase of the initial zeta-potential followed by a slight decrease with K+ concentration. The application of the DLVO theory of colloidal stability showed a growing dependence of the DLVO potential with K+ concentration and consequently a increasing stability.

Alkanes↗
PubMed2006

Effects of fluorinated and hydrogenated surfactants on human serum albumin at different pHs.

Complexation between human serum albumin (HSA) and two different surfactants, one fully fluorinated (sodium perfluorooctanoate, SPFO) and one fully hydrogenated (sodium caprylate, SO), was studied using zeta-potential measurements and difference spectroscopy. The study was carried out at three different pHs, 3.2, 6.7, and 10.0. The spectroscopy study was performed at pHs 6.7 and 10.0, given that at pH 3.2 high turbidity was observed in the wide range of surfactant concentrations. The results were interpreted in terms of the electrostatic and hydrophobic contributions to the stability of the different phases formed in the water-surfactant-HSA system. Solutions and precipitates were observed in the concentration range investigated in more detail. Using Pace methods, the thermodynamic values of the surfactant-induced conformational changes in HSA were determined for sodium perfluorooctanoate in the concentration range 2-12 mmol dm(-3) at pH 6.7 and 5-22 mmol dm(-3) at pH 10.0. Electrophoretic measurements were used to characterize surfactant adsorption by determining the number of molecules adsorbed on the surface of HSA and the Gibbs energy of adsorption. Finally, the interactions between human serum albumin and other anionic surfactants studied by other authors were compared with those observed in the present work.

Electrophoresis↗
PubMed2005

Ultraviolet-circular dichroism spectroscopy and potentiometric study of the interaction between human serum albumin and sodium perfluorooctanoate.

The interaction of a fluorinated surfactant, sodium perfluorooctanoate, with human serum albumin (HSA) has been investigated by a combination of ultraviolet-circular dichroism (UV-CD) spectroscopy and potentiometry (by a home-built ion-selective electrode) techniques to detect and characterize the conformational transitions of HSA. By using difference spectroscopy, the transition was followed as a function of temperature, and the data were analyzed to obtain the parameters characterizing the thermodynamics of unfolding. The results indicate that the presence of surfactant drastically changes the melting unfolding, acting as a structure stabilizer and delaying the unfolding process. Potentiometric measurements were used to determine the binding isotherms and binding capacity for this system. The isotherm shows a high affinity of surfactant molecules for HSA. The average number of surfactant molecules absorbed per protein molecule (at 28 mM of surfactant concentration) was found to be approximately 900, about 6 g of surfactant per gram of protein. The shape of the binding capacity curve and the relation between binding capacity and extend of cooperativity were examined. From these analysis, the values of g (number of ligand-binding sites), KH (Hill binding constant), and nH (Hill coefficient) were determined.

Caprylates↗
PubMed2005

On the effect of Ca2+ and La3+ on the colloidal stability of liposomes.

This work deals with the effect of Ca2+ and La3+ on the colloidal stability of phosphatidylcholine (PC) liposomes in aqueous media. As physical techniques, nephelometry, photon correlation spectroscopy, electrophoretic mobility, and surface tension were used. The theoretical predictions of the colloidal stability of liposomes were followed using the Derjaguin-Landau-Verwey-Overbeek theory. Changes in the size of liposomes and high polydispersity values were observed as La3+ concentration increases, suggesting that this cation induces the aggregation of liposomes. However, changes in polydispersity were not observed with Ca2+, suggesting a coalescence mechanism or fusion of liposomes. The stability factor (W), calculated from the nephelometry measurements indicated that aggregation/fusion occurs at a critical concentration (c.c.) of 0.3 and 0.7 M for La3+ and Ca2+, respectively. To gain a better insight into the interaction mechanism between the liposomes and the studied ions, the interaction between PC monolayers and Ca2+ and La3+ was studied. Changes in the surface area per lipid molecule (A0) in the monolayer at the c.c. values were found for both ions, with a more pronounced effect in the case of Ca2+. This corresponds with a larger reduction of the steric repulsive interaction between the headgroups at the phospholipid membrane (pi(head)). The experimental result validates the hypothesis made on the liposome fusion in the presence of Ca2+ and liposome aggregation in the presence of La3+. These aggregation mechanisms have also been confirmed by transmission electron microscopy.

Calcium↗
PubMed2005

Thermodynamics of micellization of tetraethylammonium perfluorooctylsulfonate in water.

Conductivity, density, and sound velocity measurements as functions of temperature were made on tetraethylammonium perfluorooctylsulfonate solutions to determine the Krafft point, the dependence on temperature of the critical micelle concentration, the micellar ionization degree, and several thermodynamic properties: Gibbs free energy, enthalpy and entropy of micellization, apparent molar partial volume, thermal expansion coefficient, and the adiabatic compressibility factor of both micellized and unmicellized surfactants. Important changes occur at about 30 degrees C. Results are interpreted on the basis of dehydration of surfactant on micellization and on temperature increase.

Alkanesulfonic Acids↗
PubMed2005

The critical micelle concentration of tetraethylammonium perfluorooctylsulfonate in water.

The aggregation characteristics of tetraethylammonium perfluorooctylsulfonate in water were studied by several techniques: conductivity, pH, ion-selective electrodes, and surface tension. It was concluded that the aggregation process is gradual and starts with the formation of oligomers such as ion pairs that grow to give spherical micelles, which become wormlike with increasing concentration. Because of the size and hydrophobicity of the counterion, micelles quickly increase in ionization degree up to about 0.5. Differences among different critical micelle concentration values in the literature are explained on the basis of the gradual formation of micelles.

Journal Article↗
PubMed2005

Conformational changes in human serum albumin induced by sodium perfluorooctanoate in aqueous solutions.

Conformational changes in the bulk solution and at the air-aqueous interface of human serum albumin (HSA) induced by changes in concentration of sodium perfluorooctanoate (C(7)F(15)COO(-)Na(+)) were studied by difference spectroscopy, zeta-potential data, and axisymmetric drop shape analysis. zeta-potential was used to monitor the formation of the HSA-C(7)F(15)COO(-)Na(+) complex and the surface charge of the complex. The conformational transition of HSA in the bulk solution was followed as a function of denaturant concentration by absorbance measurements at 280 nm. The data were analyzed to obtain values for the Gibbs energies of the transition in water (DeltaG(0)(W)) and in a hydrophobic environment (DeltaG(0)(hc)) pertaining to saturated protein-surfactant complexes. The conformational changes that surfactants induce in HSA molecules alter its absorption behavior at the air-water interface. Dynamic surface measurements were used to evaluate this behavior. At low [C(7)F(15)COO(-)Na(+)], proteins present three adsorption regimes: induction time, monolayer saturation, and interfacial gelation. When surfactant concentration increases and conformational changes in the bulk solution occur, the adsorption regimes disappear. HSA molecules in an intermediate conformational state migrate to the air-water interface and form a unique monolayer. At high [C(7)F(15)COO(-)Na(+)], the adsorption of denatured molecules exhibits a behavior analogous to that of dilute solutions.

Caprylates↗
PubMed2005

A comparative study of the physicochemical properties of perfluorinated and hydrogenated amphiphiles.

In this work we studied and compared the physicochemical properties of perfluorinated (sodium perfluoroheptanoate, C7FONa, and perfluorooctanoate, C8FONa) and hydrogenated (sodium octanoate, C8HONa, decanoate, C10HONa, and dodecanoate, C12HONa) amphiphiles. First, we determined their Krafft points to study the solubility and appropriate temperature range of micellization of these compounds. The critical micelle concentration (cmc) and ionization degree of micellization (beta) as a function of temperature (T) were estimated from conductivity data. Plots of cmc vs T appear to follow the typical U-shaped curve with a minimum T(min). The results show that the surfactants with CF2/CH2 ratio of 1.5 between alkyl chains (C12HONa-C8FONa and C10HONa-C7FONa) have nearly the same minimum value for cmc against temperature. The comparison between the cmc of hydrogenated amphiphiles and the corresponding perfluorinated amphiphiles must be done at this point. Thermodynamic functions of micellization were obtained by applying different theoretical models and choosing the one that best fit our experimental data. Although perfluorinated and hydrogenated amphiphiles present similar thermodynamic behavior, we have found a variation of 1.3 to 1.7 in the CF2/CH2 ratio, which did not remain constant with temperature. In the second part of this study the apparent molar volumes and adiabatic compressibilities were determined from density and ultrasound velocity measurements. Apparent molar volumes at infinite dilution presented the ratio 1.5 between alkyl chains again. However, apparent molar volumes upon micellization for sodium perfluoroheptanoate indicated a different aggregation pattern.

Algorithms↗
PubMed2004

Structural micellar transition for fluorinated and hydrogenated sodium carboxylates induced by solubilization of benzyl alcohol.

The solubility of benzyl alcohol in micellar solutions of sodium octanoate and sodium perfluorooctanoate was studied. From the isotherms of specific conductivity versus molality at different alcohol concentrations, the critical micelle concentration and the degree of ionization of the micelles were determined. The cmc linearly decreases upon increasing the amount of benzyl alcohol present in aqueous solutions with two distinct slopes. This phenomenon was interpreted as a clustering of alcohol molecules above a critical point, around 0.1 mol kg(-1). Attending to the equivalent conductivity versus square root of molality, the presence of a second micellar structure for the fluorinated compound was assumed. The thermodynamic parameters associated with the process of micellization were estimated by applying Motomura's model for binary surfactant mixtures, modified by Pérez-Villar et al. (Colloid Polym. Sci 1990, 268, 965) for the case of alcohol-surfactant solutions. A comparison of the hydrogenated and fluorinated compounds was carried out and discussed.

Journal Article↗
PubMed2003

Study of the interactions between lysozyme and a fully-fluorinated surfactant in aqueous solution at different surfactant-protein ratios.

The interactions of a fluorinated surfactant, sodium perfluorooctanoate, with lysozyme, have been investigated by a combination of UV absorbance, electrical conductivity and dynamic light scattering to detect and to characterize the conformational transitions of lysozyme. By using difference spectroscopy, the transition was followed as a function of surfactant concentration, and the data were analyzed to obtain the Gibbs energy of the transition in water (DeltaGw(o)) and in a hydrophobic environment (DeltaGh(o)) for saturated protein-surfactant complexes. Electrical conductivity was used to determine the critical micelle concentration of the surfactant in the presence of different lysozyme concentration. From these results, the average number of surfactant monomer per protein molecule was calculated. Finally, dynamic light scattering show that only changes in the secondary structure of the protein can be observed.

Caprylates↗
PubMed2003

Interactions between liposomes and cations in aqueous solution.

An investigation on the dependence of electrophoretic mobilities of unilamellar vesicles of phosphatidylcholine-cholesterol-phosphatidylinositol (PC-Chol-PI) on the concentration of several cations with variations in the relation charge/radius in the range Na+, K+, Cs+, Mg2+, Ca2+, Ba2+, Al3+, and La3+ has been realized. Plots of zeta potential against ion concentration exhibit a maximum for all the cations under study, the position of the maximum is greatly affected by the charge of the ion. From the feature of these plots two phenomenon were observed: an initial binding of cations into the slipping plane for ion concentration below the maximum and a phenomenon of vesicle association for concentration above the maximum. To confirm these observations measurements on dynamic light scattering were performed to obtain the corresponding size distribution of the liposomes at different ion concentrations. Finally the ability of the Stern isotherm to describe the adsorption of the cations to vesicles was tested by two methods. The two main parameters of the theory: the total number of adsorption sites per unit area, N1, and the equilibrium constant, K; (and consequently the free energy of adsorption, deltaG0ads) were calculated for the different ions, showing good agreement. The equilibrium constants of adsorption have been found to obey a linear relationship with ion radius the slope of which decreases with the ion charge.

Cations↗
PubMed2003

The effect of item feedback on multiple-choice test responses.

This study examines the effects of item feedback on multiple-choice test responses. In the first experiment, a positive effect was predicted under instructions advising a penalty for errors; a larger beneficial effect on female scores was expected, given the (presumed) tendency of female participants toward omission when uncertain. Feedback effects were either negligible or negative, and the expected interaction effect with gender was not found. The second experiment was a high-powered replication of the feedback effect on errors, controlling for participants' ability. The discussion takes into account other evidence to state that recommendations of providing item feedback in the context of testing are neither theoretically nor empirically founded.

Adult↗