title: Spontaneous formation of densely stacked multilamellar vesicles in dioctadecyldimethylammonium bromide/oleosiloxane mixtures.
abstract: A double-tailed surfactant, for example, dioctadecyldimethylammonium bromide (DODAB), tends to form bilayer fragments rather than vesicles in aqueous solution upon sonication. This Letter reports on the morphological transformations of the membrane fragments leading to multilamellar vesicle formation. The surfactant membranes were swollen with tetra(11-methoxy-11-oxoundecyl)tetramethylcyclotetrasiloxane (3) (a cyclosiloxane with covalently attached fatty-acid esters) up to 50 mol % based on the surfactant content. That compound was synthesized by hydrosilylation of 1,3,5,7-tetramethylcyclotetrasiloxane with four molecules of methyl undec-10-enoate. Using cryo-transmission electron microscopy (cryo-TEM), it has been shown that densely stacked multilamellar vesicles form spontaneously in the sonicated DODAB dispersion containing 50 mol % of the compound 3 after adjusting pH to the value of 9.5. This occurs as a result of the hydrolysis of ester bonds of the compound 3 inside the membrane with formation of tetra(11-carboxyundecyl)tetramethylcyclotetrasiloxane (4). The carboxylic groups in compound 4 are ionized under experimental conditions. That results in the appearance of the negative charge at the surface which neutralizes the positively charged molecules of DODAB, thus reducing repulsive interactions between the membrane fragments. Additionally, as was shown using Langmuir monolayer measurements, the presence of compound 4 expands the DODAB film and decreases its bending rigidity. That makes the bending process considerably easier and promotes formation of multilamellar vesicles.
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland. kepczyns@chemia.uj.edu.pl
authors.forename: Mariusz
authors.initials: M
authors.lastname: Kepczynski
authors.forename: Jan
authors.initials: J
authors.lastname: Bednar
authors.forename: Danuta
authors.initials: D
authors.lastname: Kuźmicz
authors.forename: Paweł
authors.initials: P
authors.lastname: Wydro
authors.forename: Maria
authors.initials: M
authors.lastname: Nowakowska
mesh_terms: D004952:Esters / Q000737:chemistry; D005227:Fatty Acids / Q000737:chemistry; D006868:Hydrolysis; D008567:Membranes, Artificial; D046529:Microscopy, Electron, Transmission; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry; D012833:Siloxanes / Q000737:chemistry*
chemical_list: D004952:Esters; D005227:Fatty Acids; D008567:Membranes, Artificial; D000644:Quaternary Ammonium Compounds; D012833:Siloxanes; C026584:dioctadecyltrimethylammonium; D012822:Silicon Dioxide