Polymeric surfactant vesicles. Synthesis and characterization by nuclear magnetic resonance spectroscopy and dynamic laser light scattering

Abstract

(CH/sub 3/(CH/sub 2/)/sub 15/)(CH/sub 2/==CH(CH/sub 2/)/sub 8/CONH(CH/sub 2/)/sub 6/)(CH/sub 3/)/sub 2/N/sup +/Br/sup -/(1),(CH/sub 3/(CH/sub 2/)/sub 14/CO/sub 2/(CH/sub 2/)/sub 2/)/sub 2/(CH/sub 3/)(CH/sub 2/CH==CH/sub 2/)N/sup +/Br/sup -/(2),(CH/sub 3/(CH/sub 2/)/sub 14/CO/sub 2/(CH/sub 2/)/sub 2/)/sub 2/NCOCH==CHCO/sub 2/H(3), and (CH/sub 3/(CH/sub 2/)/sub 17/)NCOCH==CHCO/sub 2/H(4) have been synthesized. Sonication of these surfactants led to the formation of vesicles. Vesicles could be polymerized by exposure to ultraviolet radiation or by the use of azoisobutyronitrile (AIBN) as an initiator. Vesicles prepared from 1 polymerized in their bilayers. Vesicles prepared from 2, 3, and 4 have double bonds on their headgroups and could, therefore, potentially polymerize both at the inner and outer surfaces or separately at either surface. Polymerization of vesicles prepared from 2, 3, and 4 by ultraviolet radiation resulted in the closing of both surfaces. Conversely, addition of AIBN to a solution of these vesicles and subsequent incubation at 80/sup 0/ led to the selective ''zipping-up'' of the outer surface only. Following the loss of vinyl protons of the surfactant vesicles by /sup 1/HNMR spectroscopy provided evidence for polymerization. Presence of vesicles has been demonstrated by substrate entrapment, gel filtration, and dynamic laser light scattering. Increasing the sonication time led to smaller and less polydisperse vesicles. Onmore » polymerization, vesicles maintaned the sizes of their nonpolymeric counterparts. Polymeric vesicles were found to be appreciably more stable than their unpolymerized analogues. Polymeric vesicles retained the fluidities of vesicles and underwent thermotropic phase transitions. Addition of KCl led to the growth of both unpolymerized and polymeric surfactant vesicles.« less