title: Thermodynamic Analysis of the Transition of Liquid Crystals from Lamellar to Vesicular Phase.
abstract: Here, we report the results of thermodynamic analyses on the lamellar-vesicular transition for a cationic amphiphilic species, namely 2-hydroxyethyl di(alkanol)oxyethyl methylammonium methylsulfate (DEAE). Previously, we have shown that spontaneous vesicle formation from a Lα-lamellar liquid crystal (LC) phase only occurs on the addition of a quantitative amount of additives to the DEAE LC at certain temperatures and that this change occurs without the input of any extra mechanical energy. These lamellar-vesicular transitions occur in two steps: the first step is the formation of an excited state, caused by the solubilization of organic substances in the bilayer structure. The second step, induced by the addition of a small amount of inorganic salt to the excited LC state, is the transition from lamellar to vesicular phase. From our experimental data, the change in the Gibbs free energy was estimated by assuming an ideal electrical chemical potential. As a result, the thermodynamic parameters at 303 K for the lamellar-vesicular transition from the initial state (lamellar) to the final state (vesicle) were found to be approximately -2.7 kJ/mol for the Gibbs free energy, -14.6 kJ/mol for the enthalpy change, and -11.9 kJ/mol for the entropy change. Each state change was due to structural changes not only in the LC bilayers but also in the hydration structure of the surrounding water. Moreover, the most significant finding is that the free energy change in lamellar-vesicular transition is negative, which may be explained based on the stabilization of solubilized vesicles with respect to the unsolubilized lamellar phases.
authors.affiliation: Graduate School of Applied Chemistry, Kanagawa University.
authors.forename: Yasutaka
authors.initials: Y
authors.lastname: Enomoto
authors.forename: Yoko
authors.initials: Y
authors.lastname: Imai
authors.forename: Kazuo
authors.initials: K
authors.lastname: Tajima
mesh_terms: D002122:Calcium Chloride / Q000737:chemistry; D053138:Cyclohexenes / Q000737:chemistry; D004735:Energy Transfer; D000077222:Limonene; D050866:Liquid Crystals / Q000737:chemistry*; D044367:Phase Transition; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D013463:Sulfuric Acid Esters / Q000737:chemistry*; D013729:Terpenes / Q000737:chemistry; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D053138:Cyclohexenes; D000644:Quaternary Ammonium Compounds; D013463:Sulfuric Acid Esters; D013729:Terpenes; D014867:Water; D000077222:Limonene; D002122:Calcium Chloride; C033522:methyl sulfate