Norio Saito1, Sekito Itoyama2, Yukishige Kondo3. 1. Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan. Electronic address: nsaito@rs.tus.ac.jp. 2. Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan. 3. Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan. Electronic address: ykondo@rs.tus.ac.jp.
Abstract
HYPOTHESIS: Novel photoresponsive hybrid surfactants, in which a combination of perfluoroalkyl and alkyl chains and cationic head groups are connected via azobenzene moieties, are excellent candidates for assembling low-molecular-weight organogels (LMOGs) with reversibly switchable viscoelasticities triggered by external stimuli. EXPERIMENTS: The structure-composition-property relationships of gels assembled with the hybrid surfactants were investigated by UV-vis and NMR spectroscopy, SEM, XRD, and rheology. FINDINGS: Hybrid surfactants containing perfluorohexyl chains with more than six carbons gelled in a variety of organic solvents at concentrations of less than a few percent. In particular, compositions with the perfluorooctyl and somewhat shorter hydrocarbon chains (C1-C4) gelled in both organic solvents and water. The gellable solvent species can be well grouped according to their solubility parameters, suggesting that gelation properties can be predicted from the chemical structure of the surfactant. Mechanical and structural investigations revealed that gel viscoelasticity can be reversibly altered by applying photo, shear, and heat stimuli, which is achieved through the formation and deformation of lamella-like molecular aggregates. The multi-responsive gelation and facile molecular design of the present hybrid surfactants will expand the fields in which fluorinated LMOGs can be applied.
HYPOTHESIS: Novel photoresponsive hybrid surfactants, in which a combination of perfluoroalkyl and alkyl chains and cationic head groups are connected via azobenzene moieties, are excellent candidates for assembling low-molecular-weight organogels (LMOGs) with reversibly switchable viscoelasticities triggered by external stimuli. EXPERIMENTS: The structure-composition-property relationships of gels assembled with the hybrid surfactants were investigated by UV-vis and NMR spectroscopy, SEM, XRD, and rheology. FINDINGS: Hybrid surfactants containing perfluorohexyl chains with more than six carbons gelled in a variety of organic solvents at concentrations of less than a few percent. In particular, compositions with the perfluorooctyl and somewhat shorter hydrocarbon chains (C1-C4) gelled in both organic solvents and water. The gellable solvent species can be well grouped according to their solubility parameters, suggesting that gelation properties can be predicted from the chemical structure of the surfactant. Mechanical and structural investigations revealed that gel viscoelasticity can be reversibly altered by applying photo, shear, and heat stimuli, which is achieved through the formation and deformation of lamella-like molecular aggregates. The multi-responsive gelation and facile molecular design of the present hybrid surfactants will expand the fields in which fluorinated LMOGs can be applied.