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ABSTRACT: The line tension (λ) in biphasic membranes has been determined in monolayers and bilayers using a variety of techniques. In this work we present a novel approach to the determination of λ in monolayers with liquid/liquid phase coexistence, overcoming several of the drawbacks of current techniques. Using our method, we determined the line tension of liquid/liquid phases in binary mixtures of different lipids and a molecule similar to cholesterol but less oxidizable. We analyzed the effect of the hydrocarbon chain length and the polar head-group of the non-sterol lipid and found the latter to exert much more influence than the former. The presence of PE led to high λ values, PG to low values and PS and PC to intermediate values. The line tension showed a strong correlation with the critical packing parameter of the phospholipid. The spontaneous curvature displayed by the phases constituted by a particular lipid appears to be an important parameter for determining the line tension in mixed films.
Chemistry and physics of lipids 09/2012; 165(7):737-744. · 2.15 Impact Factor
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ABSTRACT: Biomembranes contain a wide variety of lipids and proteins within an essentially two-dimensional structure. The coexistence
of such a large number of molecular species causes local tensions that frequently relax into a phase or compositional immiscibility
along the lateral and transverse planes of the interface. As a consequence, a substantial microheterogeneity of the surface
topography develops and that depends not only on the lipid–protein composition, but also on the lateral and transverse tensions
generated as a consequence of molecular interactions. The presence of proteins, and immiscibility among lipids, constitute
major perturbing factors for the membrane sculpturing both in terms of its surface topography and dynamics. In this work,
we will summarize some recent evidences for the involvement of membrane-associated, both extrinsic and amphitropic, proteins
as well as membrane-active phosphohydrolytic enzymes and sphingolipids in driving lateral segregation of phase domains thus
determining long-range surface topography.
Cell Biochemistry and Biophysics 04/2012; 50(2):79-109. · 3.74 Impact Factor
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ABSTRACT: The phase diagram of mixed monolayers composed of dimyristoyl phosphatidylcholine (DMPC) and stearic acid (SA) on different subphases was previously reported. It was observed that on acid subphases, liquid-condensed domains with shapes that depend on the SA proportion are formed. For mixtures with 40-45mole% of SA, the domain shape changes from flower-like to circular domains. In this work, we carried out a detailed study of the driving force for the shape change. We find that it is related to the domain density which, in turn, is driven by the domain nucleation process and thus by oversaturation of the system leading to phase segregation. This could be a way of self-regulating the local electrostatics and mechanical properties in membrane surfaces with segregated phase domains.
Chemistry and physics of lipids 02/2012; 165(2):232-7. · 2.15 Impact Factor
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ABSTRACT: In a previous work, Muruganathan and Fischer observed laser-induced local collapse of a methyl stearate monolayer. These experiments opened the possibility of studying the collapse mechanism in a highly controlled manner, since the laser intensity can be easily varied and collapse happens in a definite place (the laser focus). In this paper we extended the work presented by Muruganathan et al., describing the local yielding as an alternative pathway toward monolayer collapse competing with the global collapse of the monolayer. We first corroborated that the laser-induced collapse is a thermocapillary effect and afterward determined the threshold laser power necessary for the local pathway to win over the global collapse. We show that the laser threshold is determined more by the gradients in temperature and pressure than by the global pressure and temperature. We propose that the flow of material into the focus of the laser is observed after the yield stress of the monolayer is overcome. The higher the yield stress, the higher the temperature gradient that is necessary for the monolayer to yield. The local pathway opens only when the derivative of surface pressure with temperature is negative such that stress gradients point toward the laser focus and a sink of material is generated. In such a case we are able to give estimates of the dilatational yield pressure of the solid monolayer.
The Journal of Physical Chemistry B 08/2011; 115(40):11631-7. · 3.70 Impact Factor
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ABSTRACT: Ascorbyl palmitate (ASC(16)) is a molecule of potential pharmacological interest due to its antioxidant properties and amphiphilic nature. The surface behavior of ASC(16) was studied using Langmuir monolayers and Brewster angle microscopy. This molecule formed stable monolayers at room temperature that showed phase transition from a liquid-expanded to liquid-condensed or crystalline phase, depending on the subphase conditions. Using a theoretical approach, we were able to explain the behavior of the ASC(16) film at different bulk pH values and salt conditions based on the surface pH and the dissociation fraction of the film. Both condensed phases corresponded to highly packed conditions with the crystalline phase occurring at a low charge density, showing molecular tilting and preferential growth at characteristic angles, while the liquid-condensed phase formed in highly charged surfaces revealed small flowerlike domains probably as a consequence of internal dipole repulsion. A smaller perpendicular dipole moment was observed for the crystalline than the liquid-condensed phase which may explain the domain features. In conclusion, ASC(16) showed a complex surface behavior that was highly sensitive to subphase conditions.
Langmuir 07/2011; 27(17):10914-9. · 4.19 Impact Factor
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ABSTRACT: The aim of this work is to study the phase diagram of mixed monolayers composed of dimyristoylphosphatidylcholine (DMPC) and stearic acid (SA) at different ionic strength and bulk pH of the aqueous subphase. In this way, the effect of ionization of SA on the interaction and thus on phase separation with the DMPC matrix can be analyzed. To this purpose, we first determined the ionization state of pure SA monolayers as a function of the bulk subphase pH. The SA monolayers are nearly fully ionized at pH 10 and essentially neutral at pH 4 and the mixture of DMPC and SA was studied at those two pHs. We found that the DMPC-enriched phase admits more SA if the SA monolayer is in a liquid-expanded state, which is highly related to the acid ionization state, and thus to the bulk pH and ionic strength. At pH 4 the molecules hardly mix while at pH 10 the mixed monolayer with DMPC can admit between 30 and 100% of SA (depending on the lateral pressure) before phase separation is established. The addition of calcium ions to the subphase has a condensing effect on SA monolayers at all pHs and the solubility of SA in the DMPC matrix does not depend on the bulk pH in these conditions. The observed phase diagrams are independent on the manner in which the state of the mixed film is reached and may thus be considered states of apparent equilibrium.
Chemistry and physics of lipids 05/2011; 164(5):386-92. · 2.15 Impact Factor
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ABSTRACT: Diacylglycerol pyrophosphate (DGPP), a phosphorylated form of phosphatidic acid (PA), gained attention recently due to its role as signaling lipid. However, little is known about its surface organization and potential impact on membrane-mediated function. In this work we investigated the interfacial behavior of Langmuir monolayers formed with pure DGPP and of its mixtures with PA. We found that changes of the subphase pH affect the surface behavior of DGPP. At pH 8, DGPP forms liquid expanded monolayers with a compressibility modulus of about 60mNm⁻¹ at collapse. On acidic solutions, the compressibility modulus increases to 90mNm⁻¹ and the average molecular area is smaller. At pH 8, DGPP and its precursor PA form thermodynamically favored topographically homogeneous non-ideal mixtures. The interaction among these lipids leads to a non-ideal diminution of the mean molecular area and consequently, to an increase of the compressibility modulus, with variations of the surface electrostatics. The favorable interaction of PA and DGPP, leading to changes of the film packing suggest that DGPP may act as a structural signal transducer in membrane-mediated cellular processes.
Chemistry and physics of lipids 11/2010; 163(8):771-7. · 2.15 Impact Factor
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ABSTRACT: Biomembranes contain a wide variety of lipids and proteins within an essentially two-dimensional structure. The coexistence of such a large number of molecular species causes local tensions that frequently relax into a phase or compositional immiscibility along the lateral and transverse planes of the interface. As a consequence, a substantial microheterogeneity of the surface topography develops and that depends not only on the lipid-protein composition, but also on the lateral and transverse tensions generated as a consequence of molecular interactions. The presence of proteins, and immiscibility among lipids, constitute major perturbing factors for the membrane sculpturing both in terms of its surface topography and dynamics. In this work, we will summarize some recent evidences for the involvement of membrane-associated, both extrinsic and amphitropic, proteins as well as membrane-active phosphohydrolytic enzymes and sphingolipids in driving lateral segregation of phase domains thus determining long-range surface topography.
Cell Biochemistry and Biophysics 02/2008; 50(2):79-109. · 3.74 Impact Factor
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ABSTRACT: Lipid and protein molecules anisotropically oriented at a hydrocarbon-aqueous interface configure a dynamic array of self-organized molecular dipoles. Electrostatic fields applied to lipid monolayers have been shown to induce in-plane migration of domains or phase separation in a homogeneous system. In this work, we have investigated the effect of externally applied electrostatic fields on the distribution of the condensed ceramide-enriched domains in mixed monolayers with sphingomyelin. In these monolayers, the lipids segregate in different phases at all pressures. This allows analyzing by epifluorescence microscopy the effect of the electrostatic field at all lateral pressure because coexistence of lipid domains in condensed state are always present. Our observations indicate that a positive potential applied to an electrode placed over the monolayer promotes a repulsion of the ceramide-enriched domains which is rather insensitive to the film composition, depends inversely on the lateral pressure and exhibits threshold dependence on the in-plane elasticity.
Biophysical Chemistry 07/2006; 122(1):36-42. · 2.20 Impact Factor
