Phase Transitions and Spatially Ordered Counterion Association in Ionic-Lipid Membranes: Theory versus Experiment

• Published in: Langmuir Vol. 27; no. 21; pp. 13130 - 13143
• Main Authors: Henriques, V. B, Germano, R, Lamy, M. T, Tamashiro, M. N
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.11.2011
• Subjects: Biological Interfaces: Biocolloids, Biomolecular and Biomimetic Materials; Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Membranes; Phase diagram; Theory; Electrokinetics; Lipids; Hydrophobicity; Phase transitions; Association; Phosphatidylglycerol; Membrane; Electrostatic repulsion; Differential scanning calorimetry; Experimental data; Melting; Electrical properties; Light scattering; Chain length; Conductivity; Bilayer; Electrolyte; Ionic strength; Electrophoretic mobility; Statistical model; Van der Waals interaction; Counter ion; Aqueous dispersion
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la202302x

Aqueous dispersions of phosphatidylglycerol (PG) lipids may present an anomalous chain-melting transition at low ionic strengths, as seen by different experimental techniques such as calorimetry or light scattering. The anomaly disappears at high ionic strengths or for longer acyl-chain lengths. In this article, we use a statistical model for the bilayer that distinguishes both lipid chain and headgroup states in order to compare model and experimental thermotropic and electrical properties. The effective van der Waals interactions among hydrophobic chains compete with the electrostatic repulsions between polar headgroups, which may be ionized (counterion dissociated) or electrically neutral (associated with counterions). Electric degrees of freedom introduce new thermotropic charge-ordered phases in which headgroup charges may be spatially ordered, depending on the electrolyte ionic strength, introducing a new rationale for experimental data on PGs. The thermal phases presented by the model for different chain lengths, at fixed ionic strength, compare well with an experimental phase diagram constructed on the basis of differential scanning calorimetry profiles. In the case of dispersions of DMPG (dimyristoyl phosphatidylglycerol) with added monovalent salt, the model properties reproduce the main features displayed by data from differential scanning calorimetry as well as the characteristic profile for the degree of ionization of the bilayer surface across the anomalous transition region, obtained from the theoretical interpretation of electrokinetic (conductivity and electrophoretic mobility) measurements.