The aggregation behaviors of a series of dissymmetric cationic Gemini surfactants, [C(m)H(2m+1)(CH(3))(2)N(CH(2))(2)N(CH(3))(2)C(n)H(2n+1)]Br(2), designated as m-2-n (with a fixed m + n = 24, m = 16, 14, 12) have been investigated in a protic ionic liquid, ethylammonium nitrate (EAN). Surface tension, polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and rheological measurements are adopted to investigate the micellization and lyotropic liquid crystal (LLC) formation. The obtained results indicate that the structure dissymmetry plays an important role in aggregation process of m-2-n. With increasing degree of dissymmetry, the critical micellization concentration, the maximum reduction of solvent surface tension, and the minimum area occupied per surfactant molecule at the air/EAN interface all become smaller. The thermostability of formed LLCs is therefore improved because of the more compact molecules. These characteristics can be explained by the enhancement of solvophobic effect due to the increased structure dissymmetry of Gemini surfactants.
Two different room-temperature ionic liquids (ILs), the protic ethylammonium nitrate (EAN) and the aprotic 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF(4)), have been employed to investigate the solvent protonation effect on aggregation behaviors of a phytosterol ethoxylate surfactant (BPS-10). The calculated thermodynamic parameters based on surface tension measurements present a stronger solvophobic interaction in EAN than that in [Bmim]BF(4) and disclose different driving forces for micelle formation. In addition, the polarized optical microscopy and small-angle X-ray scattering techniques are used to characterize the phase structures formed in both systems at 25 °C. Due to the H-bonding networks in protic EAN, BPS-10 exhibits a lyotropic liquid-crystalline behavior different from that in [Bmim]BF(4). Results obtained from the rheological measurements reflect a more viscoelastic nature of lyotropic liquid-crystalline phases in EAN. The obtained results indicate that the protic EAN behaves more effective than [Bmim]BF(4) to promote the nonionic BPS-10 aggregation.
A novel photo-responsive anionic surfactant with a dimethylamino-substituted azobenzene located at the end of the hydrophobic chain, 6-(4-dimethylaminoazobenzene-4'-oxy)hexanoate sodium (DAH), has been designed. Through the host-guest interaction in aqueous solution, the trans-DAH could be spontaneously included by using two native α-cyclodextrin (α-CD) molecules. The formed hydrophilic inclusion complex (DAH@2α-CD), however, could act as a gelator to induce the formation of a supramolecular hydrogel, which is driven mainly by hydrogen bonds between neighboring α-CDs and also between the carboxylate in DAH and water. Compared with common hydrogels that consist of networks with fibres or discrete polymer chains, the hydrogel formed by DAH@2α-CD was composed of periodic lamellar structures possessing good shear-thinning behavior and much swollen water layers. The more interesting point for such a hydrogel was its visible-light responsibility for gel-sol reversible phase transition. This originated from the introduction of an electron-donating group (dimethylamino) to azobenzene, which noticeably red-shifted the responsive wavelength for its trans-to-cis isomerization. It was also worth noting that the host-guest interaction between azobenzene in DAH and α-CD significantly improved the photo-transition efficiency from trans to cis forms of azobenzene, which played a critical role in the visible-light responsibility of the hydrogel. This unique visible-light-responsive behavior combined with the inherent thermo-responsive property from α-CD should make the prepared hydrogel find more potential applications in biomedical systems.
The aggregation behavior of Gemini surfactants with hydroxyl groups in their headgroups, butane-1,4-bis(hydroxyethyl methylalkylammonium) bromides hereafter abbreviated as m-4-m MEA (m = 12, 14, 16), has been investigated in aqueous solution. Each formed a viscous fluid in water at low concentration in the absence of a salt. In solutions of 14-4-14 MEA, the formation of highly viscoelastic wormlike micelles could be detected using steady and dynamic rheological measurements. The existence of these long column micelles has also been confirmed using cryo-transmission electron microscopy (cryo-TEM) and small angle X-ray scattering (SAXS). Compared with conventional bis(dimethylalkylammonium) bromide Gemini molecules with the same spacer (14-4-14), 14-4-14 MEA demonstrated a better ability to fabricate wormlike micelles because of the change in the headgroup structure. As for 16-4-16 MEA, which has longer alkyl chains, its aqueous solutions behave more like elastic gels at a concentration of 80 mmol L(−1). The unique viscoelastic behavior of m-4-m MEA in water can be attributed to the synergistic interactions of hydrophobic attraction and hydrogen bonding. The obtained results are believed to be an important addition to the effect that the headgroups of Gemini surfactants have on their aggregation behavior in dilute solutions.
The aggregation behaviors of a Gemini surfactant [C12H25(CH3)2N(+)(CH2)2N(+)(CH3)2C12H25]Br2(-) (12-2-12) in two protic ionic liquids (PILs), propylammonium nitrate (PAN) and butylammonium nitrate (BAN), were investigated by means of several experimental techniques including small and wide-angle X-ray scattering, the polarized optical microscopy and the rheological measurement. Compared to those in ethylammonium nitrate (EAN), the minor structural changes with only one or two methylene units (-CH2-) increase in cationic chain length of PIL, result in a dramatic phase transition of formed aggregates. The critical micellization concentration was increased in PAN, while no micelle formation was detected in BAN. A normal hexagonal phase was observed in the 12-2-12/PAN system, while the normal hexagonal, bicontinuous cubic, and lamellar phases were mapped in the 12-2-12/BAN system. Such aggregation behavior changes can be ascribed to the weaker solvophobic interactions of 12-2-12 in PAN and BAN. The unique molecular structure of 12-2-12 is also an important factor to highlight such a dramatic phase transition due to the PIL structure change.
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