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J Miñones

Publications and source records attributed to J Miñones.

11 recordsLinked to original sources

Study of adsorption and penetration of E2(279-298) peptide into Langmuir phospholipid monolayers.

The peptide corresponding to the sequence (279-298) of the Hepatitis G virus (HGV/GBV-C) E2 protein was synthesized, and surface activity measurements, pi-A compression isotherms, and penetration of E2(279-298) into phospholipid monolayers spread at the air-water interface were carried out on water and phosphate buffer subphases. The results obtained indicated that the pure E2(279-298) Langmuir monolayer exhibited a looser packing on saline-buffered than on pure water subphase and suggest that the increase in subphase ionic strength stabilizes the peptide monolayer. To better understand the topography of the monolayer, Brewster angle microscopy (BAM) images of pure peptide monolayers were obtained. Penetration of the peptide into the pure lipid monolayers of dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) and into mixtures of dimyristoylphosphatidylcholine/dimyristoylphosphatidylglycerol (DMPC/DMPG) at various initial surface pressures was investigated to determine the ability of these lipid monolayers to host the peptide. The higher penetration of peptide into phospholipids is attained when the monolayers are in the liquid expanded state, and the greater interaction is observed with DMPC. Furthermore, the penetration of the peptide dissolved in the subphase into these various lipid monolayers was investigated to understand the interactions between the peptide and the lipid at the air-water interface. The results obtained showed that the lipid acyl chain length is an important parameter to be taken into consideration in the study of peptide-lipid interactions.

1,2-Dipalmitoylphosphatidylcholine↗

The influence of subphase temperature on miltefosine-cholesterol mixed monolayers.

Effects of the subphase temperature on the surface pressure (pi)-area (A) isotherms of mixed monolayers of miltefosine (hexadecylphosphocholine), a potential anticancer drug, and cholesterol were investigated at the air/water interface, which were supplemented with Brewster angle microscopy (BAM) observations. Comparison of the collapse pressure values, mean molecular areas, excess areas and excess free energy of mixing between the mixed monolayer at various molar ratios and the pure component monolayers showed that, regardless of the subphase temperature, the investigated miltefosine-cholesterol system is much more stable than that the pure component monolayers, suggesting strong attractive interactions between miltefosine and cholesterol in mixed monolayers. As a consequence, it was postulated that stable "complexes" of the two components could form at the interface, for which stoichiometry may vary with the subphase temperature. Such "surface complexes" should be responsible for the contraction of the mean molecular area and thus the high stability of the mixed monolayer.

Adsorption↗

Influence of the saturation chain and head group charge of phospholipids in the interaction of hepatitis G virus synthetic peptides.

Using the Langmuir technique, we have studied the properties at the air/water interface and the interaction of the hepatitis G virus synthetic peptide E1(53-66) and its palmitoyl derivative with membrane phospholipids. These phospholipids had different characteristics referring to the net charge and saturation of the acyl chain. The palmitoyl derivative was more stable at the air/water interface and in the kinetic at constant area measurements showed higher incorporation to the monolayer. The interaction was higher for saturated phospholipids and those with a negative net charge. When the peptides were in the subphase, they produced changes in the miscibility of mixed monolayers composed of DPPC/DPPG or DOPC/DOPG. It can be deduced from the results obtained that electrostatic interactions play a major role, but when the peptide is derivatized with the palmitoyl chain, hydrophobic interactions are added to the former ones. The interaction is also influenced by the saturation of the acyl chain.

1,2-Dipalmitoylphosphatidylcholine↗

Surface behavior of oleoyl palmitoyl phosphatidyl ethanolamine (OPPE) and the characteristics of mixed OPPE-miltefosine monolayers.

Langmuir monolayers of oleoyl palmitoyl phosphatidyl ethanolamine (OPPE) were investigated at the air/water interface by means of surface pressure (pi)-area (A) isotherms complemented with Brewster angle microscopy images upon film compression/expansion. The characteristic phase transition appearing in the course of pi/A isotherms was attributed to the coexistence of two liquid-expanded phases of different molecular ordering. The interactions between OPPE and hexadecylphosphocholine (miltefosine) were studied at different subphase pHs (2, 6, and 10) at 20 degrees C and analyzed with mean molecular area (A12)-, excess area of mixing (Aexc)-, and excess free energy of mixing (DeltaGexc)-composition plots. The obtained results indicate that at pH 10, where both OPPE and miltefosine polar groups are negatively charged, attractive interactions are observed (reflected by negative deviations from ideality), contrary to expectation. This peculiar behavior is explained as being due both to water molecules, which surround negatively charged polar groups and increase the distance between them, weakening in this way the electrostatic repulsion forces; and to positively charged counterions present in the diffuse double layer, neutralizing their charge. In this way, the van der Waals attraction forces between hydrocarbon tails of both molecules predominate and are responsible for the observed negative deviations from ideal behavior. Similar explanations are given for the observed negative deviations at pH 2 where both polar groups are positively charged. At pH 6, the observed negative deviations at low surface pressures and positive deviations at high pressures are interpreted as being due to a change in orientation of polar groups upon monolayer compression.

Ethanolamines↗

Semifluorinated chains in 2D-(perfluorododecyl)-alkanes at the air/water interface.

Langmuir monolayers of a homologous series of perfluorododecyl-n-alkanes (general formula F(CF2)12(CH2)nH, abbreviated as F12Hn, where n = 6-20) are investigated through isotherms of surface pressure (pi) and electric surface potential (DeltaV) versus area (A) and quantitative Brewster angle microscopy. The investigated monolayers are found to be liquid in nature. The negative sign of the measured surface potential evidences the orientation of all the investigated molecules with their perfluorinated parts directed toward the air regardless of the length of the hydrogenated unit. Analysis of the direction of the molecular dipole moment with respect to the main axis indicates that the minimum effective dipole moment is achieved for a molecule oriented at an angle of about 35 degrees to the surface normal. The film thickness was evaluated from the relative intensity measurements. The results suggest that the F12Hn molecules are tilted to the interface in the vicinity of collapse, which is in accordance with the liquid character of their monolayers.

Air↗

Miltefosine-cholesterol interactions: a monolayer study.

Mixed Langmuir monolayers of miltefosine (hexadecylphosphocholine) and cholesterol have been investigated by recording surface pressure-area (pi-A) isotherms at different subphase pHs (2, 6, and 10) and temperatures (10, 20, 25, and 30 degrees C). The change of both pH and temperature within the investigated range does not modify significantly the behavior of mixed films. The most pronounced effect involves condensation of the miltefosine monolayer by cholesterol, which diminishes in the following order: pH 6 > pH 2 > pH 10. The analyses of pi-A and compressibility modulus dependencies indicate the existence of interactions in the investigated system; at pH 2 and 6, the strongest were found to occur for the mixed film of miltefosine molar fraction (XM) between 0.6 and 0.7 (mean value, 0.66). Such a composition corresponds to the stable complex formation wherein 2 miltefosine molecules and 1 molecule of cholesterol are strongly bound together, mainly by attractive hydrophobic forces between their apolar tails. However, at pH 10 the highest stability occurs for mixtures containing a smaller proportion of miltefosine (XM = 0.5), which means that on alkaline subphases the ability to condense the miltefosine monolayer by cholesterol is less efficient as it requires a higher proportion of cholesterol (1:1 as compared to 1:2 at pH 2 and 6) to attain the maximum stability of the mixed film. The attractive forces between miltefosine and cholesterol are also weaker at pH 10 due to a greater solvatation of the miltefosine polar group. A similar trend is observed on increasing subphase temperature, when monolayers are more expanded.

Cholesterol↗

Orientational changes in dipalmitoyl phosphatidyl glycerol Langmuir monolayers.

Dipalmitoyl phosphatidyl glycerol (DPPG) as Langmuir monolayers at the air/water interface was investigated by means of surface pressure measurements in addition to Brewster angle microscopy (BAM) during film compression/expansion. A characteristic phase transition region appeared in the course of surface pressure-area (pi-A) isotherms for monolayers spread on alkaline water or buffer subphase, while on neutral or acidic water the plateau region was absent. This phase transition region was attributed to the ionization of DPPG monolayer. It has been postulated that the ionization of the phosphatidyl glycerol group leads to its increased solvation, which probably provokes both a change in the orientation of the polar group and its deeper penetration into bulk phase. Film compression along the transition region provokes the dehydration of polar groups and subsequent change of their conformation, thus causing the DPPG molecules to emerge up to the interface. Quantitative Brewster angle microscopy (BAM) measurements revealed that along the liquid-expanded to liquid-condensed phase transition the thickness of the ionized DPPG monolayer increases by 4.2 A as a result of the conformational changes of the ionized polar groups, which tend to emerge from the bulk subphase up to the surface.

Air↗

Structural and topographical characteristics of dipalmitoyl phosphatidic acid in Langmuir monolayers.

Dipalmitoyl phosphatidic acid (DPPA) monolayers at the air-water interface were studied from surface pressure (Pi)-area (A) isotherms and at the microscopic level with Brewster angle microscopy (BAM) under different conditions of temperature, pH, and ionic strength. BAM images were recorded simultaneously with Pi-A isotherms during the monolayer compression-expansion cycles. DPPA monolayers show a structural polymorphism from the liquid-expanded (LE)-liquid-condensed (LC) transition region at lower surface pressures toward liquid-condensed and solid (S) structures at higher surface pressures. An increase in temperature, pH, or ionic strength provokes an expansion in the monolayer structure. The results obtained from the Pi-A measurements are confirmed by the monolayer topography and relative reflectivity. The measurements of relative reflectivity upon monolayer compression showed an increase in relative monolayer thickness of 1.25 and 3.3 times throughout the full monolayer compression from the liquid-expanded to the liquid-condensed and solid states, respectively.

Osmolar Concentration↗

Molecular organisation of amphotericin B at the air-water interface in the presence of sterols: a monolayer study.

Using the monolayer technique to study the surface behaviour of systems consisting of amphotericin B (AmB) and various sterols, the components were found to interact with each other. The interactions observed are accounted for by postulating that, at low surface pressures, AmB and different sterols form mixed films where the former lies parallel and the latter normal to the air-water interface in such a way that the polar groups in both components establish hydrogen bonds that lead to the formation of an AmB-sterol 'complex' of 2:1 stoichiometry at the interface. At high surface pressures, AmB molecules rearrange themselves normal to the interface; this gives rise to the Van der Waals interactions between non-polar chains of both components that vary with the nature and composition of the system. The occurrence of these hydrophobic interactions prevents the desorption of AmB into the subphase, which is consistent with the positive excess areas of mixing obtained under these surface pressure conditions. Among the four sterols studied, ergosterol exhibits the strongest interaction with AmB and beta-sitosterol the weakest. Cholesterol and stigmasterol show intermediate behaviour.

Amphotericin B↗

Surface pressure-area isotherms of mixed cyclosporin-poly(isobutylcyanoacrylate) monolayers spread at the air/water interface.

The pi-A isotherms of mixed monolayers of cyclosporin and poly(isobutylcyanoacrylate) (PIBCA) show that the molecular areas of cyclosporin and PIBCA are additive regardless of the pH of the substrate or the physical state of the monolayers. All these mixed films collapse at the same surface pressure; therefore, application of the two-dimensional phase rule implies that cyclosporin and PIBCA are immiscible at the interface. This conclusion may have important implications with regard to the formulation of PIBCA-cyclosporin nanoparticles for cyclosporin administration, though further research in this direction will require consideration of the role played by the coadjuvants used for PIBCA polymerization during nanoparticle formation.

Cyanoacrylates↗

Spectrofluorimetric study of the binding of 1-anilinonaphthalene-8-sulfonate to bovine serum albumin.

We studied the binding of the fluorescent probe 1-anilinonaphthalene-8- sulfonate to bovine serum albumin by spectrofluorimetric techniques. The binding of this probe to bovine serum albumin was via two types of sites: one with a high affinity constant but relatively fewer in number and the other with a lower affinity constant but greater in number. The number of binding sites of each type of site and their respective association constants varied with the features of the moiety and the temperature. The results indicate that the simplistic interpretation involving a single type of interaction of hydrophobic nature can no longer be supported and that additional involvement of other, nonhydrophobic types of binding should be considered. This thermodynamic study allowed calculation of changes in enthalpy, Gibbs free energy, and entropy values that are consistent with this hypothesis.

Anilino Naphthalenesulfonates↗