RESUMO
Recently, inclusion complexes formed from cyclodextrins (CDs) and surfactants have been found to play complex and important roles in supramolecular self-assembly. In this work, the self-assembly of perfluorononanoic acid (PFNA)/γ-cyclodextrin (γ-CD) in aqueous solution was investigated. The sole PFNA solution assembled into spherical uni-lamellar vesicles under certain concentrations as revealed by freeze-fracture transmission electron microscopy (FF-TEM) images. Interestingly, when γ-CD was added into the PFNA solution, one novel kind of cyclodextrin-based hydrogel with a crystal-like structure was obtained. The morphology of the hydrogels was inerratic parallel hexahedron or regular hexahedron as revealed by optical microscopy and scanning electron microscopy (SEM) measurements. Furthermore, the hydrogels were transformed into crystalline precipitates, which were composed of highly uniform tetragonal sheets with excellent crystallinity and homogeneous size distribution just by changing the γ-CD concentration. More amazingly, the crystal-like hydrogels were sensitive to shear and switched to solutions in their morphology with bar-like and rod-like aggregates and smaller square sheets under different shear rates, and the hydrogel-solution transition behavior was a reversable process. 1H NMR, Fourier transform infrared (FT-IR) and wide-angle X-ray diffraction (WXRD) measurements were performed to lead us to propose the formation mechanism of the above aggregates. Hopefully, our studies will cast new light on the fundamental investigations into the self-assembly of supramolecular systems of fluorinated surfactants and CD molecules and provide a new idea for smart material design.
RESUMO
The self-assembly of α-cyclodextrin (α-CD) mixed with a fluorocarbon surfactant, perfluorononanoic acid (PFNA), in aqueous solution was studied. Interestingly, the 1:1 inclusion complex, PFNA@α-CD, was verified to form by 1H nuclear magnetic resonance measurement. Also as the building block, the PFNA@α-CD complex was further self-assembled into worm-like micelles under lower concentrations while hydrogels were self-assembled under higher concentrations. The hydrogels were composed of unilamellar vesicles with polydisperse size, which were clearly detected by freeze-fracture transmission electron microscopy measurements. Besides, the vesicle hydrogels showed high viscoelasticities and a substantial elastic characteristic. Also as revealed by the results of Fourier transform infrared measurements, the driving force for the vesicle and worm-like micelle formation was the hydrogen bonding between α-CD molecules. Then, these vesicles were densely packed to form hydrogels. As far as we know, the self-assembly of CDs and fluorocarbon surfactants based on host-guest inclusion in aqueous solution has been limitedly reported. Our work successfully constructed hydrogels consisting of vesicles through the self-assembly of the α-CD/PFNA complex for the first time and will also provide a better understanding and enrich the fundamental research of the self-assembly behavior of the CD/fluorosurfactant complex.
RESUMO
The effects of alkyl chain length of anionic fluorinated fatty acid surfactants, CnF2n+1COOH (n = 7-11), mixed with one cationic hydrocarbon surfactant, tetradecyltrimethylammonium hydroxide (TTAOH), on the formation of polyhedral vesicle gels were investigated in aqueous solutions. On the basis of phase behavior mapping, C8F17COOH, C9F19COOH, C10F21COOH and C11F23COOH except C7F15COOH all formed polyhedral vesicle gels when they were mixed with TTAOH under certain mixed ratios, which was demonstrated by freeze-fracture transmission electron microscopy (FF-TEM) measurements. Meanwhile, the following observation was not observed: the longer the fluorinated alkyl chain, the more effective the formation of gels by fluorinated fatty acids. The formation of the faceted vesicle gels was determined both by the rigidity of the fluorinated alkyl chain and the co-crystallization of fluorocarbon chains and hydrocarbon chains, as revealed by the results of differential scanning calorimetry (DSC), wide angle X-ray scattering (WAXS) and 19F NMR measurements. Furthermore, the polyhedral vesicle gels showed high viscoelasticity, which increased clearly with increasing fluorinated alkyl chain length, indicating that the viscoelastic property of the polyhedral vesicle gel was a result of the crystalline state of the polyhedral vesicle bilayers at room temperature. As far as we know, such polyhedral vesicle gels formed from perfluorinated and hydrocarbon surfactant mixtures have been rarely reported. Our study can be a great advancement in fundamental research of surfactant vesicle gels.