Vesicle-micelle structural transition of phosphatidylcholine bilayers and Triton X-100.
The structural transition stages induced by the interaction of the non-ionic surfactant Triton X-100 on phosphatidylcholine unilamellar vesicles were studied by means of static and dynamic light-scattering, transmission-electron-microscopy (t.e.m.) and permeability changes. A linear correlation was observed between the effective surfactant/lipid molar ratios (Re) ('three-stage' model proposed for the vesicle solubilization) and the surfactant concentration throughout the process. However, this correlation was not noted for the partition coefficients of the surfactant between the bilayer and the aqueous medium (K). Thus a sharp initial K increase was observed until a maximum value was achieved for permeability alterations of 50% (initial step of bilayer saturation). Further surfactant additions resulted in a fall in the K values until 100% of bilayer permeability. Additional amounts of surfactant led to an increase in K until bilayer solubilization. Hence, a preferential incorporation of surfactant molecules into liposomes governs the initial interaction steps, leading to the initial stage of bilayer saturation with a free surfactant concentration that was lower than its critical micelle concentration (c.m.c.). Additional amounts of surfactant increased the free surfactant until the c.m.c. was reached, after which solubilization started to occur. Thus the initial step of bilayer saturation was achieved for a smaller surfactant concentration than that for the Resat, although this concentration was the minimum needed for solubilization to start. Large unilamellar vesicles began to form as the surfactant exceeded 15 mol% (50% bilayer permeability), the maximum vesicle growth being attained for 22 mol% (400 nm). Thereafter, static light-scattering started to decrease gradually, this fall being more pronounced after 40 mol%. The t.e.m. picture for 40 mol% (Resat.) showed unilamellar vesicles, although with traces of smaller structures. From 50 mol% the size distribution curves began to show a bimodal distribution. The t.e.m. pictures for 50-64 mol% revealed tubular structures, together with open bilayer fragments. Thereafter, increasing amounts of surfactant (65-69 mol%) led to planar multilayered structures which gradually tended to form concentric and helicoidal conformations. The scattered intensity decreased to a low constant value at more than 71-72 mol%. However, the surfactant concentration for the Re(sol) (72.6 mol %) still presented traces of aggregated structures, albeit with mono-modal size-distribution curves (particle size of 50 nm). This vesicle size corresponded to the liposome solubilization via mixed-micelle formation.
Departamento de Tensioactivos, Centro de Investigación y Desarrollo (C.I.D.), Barcelona, Spain.
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De la Maza
J L
JL
Parra
D008027:Light; D008051:Lipid Bilayers; D008081:Liposomes; D008823:Micelles; D008854:Microscopy, Electron; D017830:Octoxynol; D010713:Phosphatidylcholines / Q000737:chemistry*; D012542:Scattering, Radiation
D008051:Lipid Bilayers; D008081:Liposomes; D008823:Micelles; D010713:Phosphatidylcholines; D017830:Octoxynol