A novel redox-switchable wormlike micellar system was developed based on a mixture of selenium-containing zwitterionic surfactant and commercially available anionic surfactant sodium dodecyl sulfate, which reversibly and quickly responds to H2O2 and vitamin C, and shows circulatory gel/sol transition, reflecting changes in aggregate morphology from entangled worms to vesicles.

Control of interfacial properties (foaming and emulsification) plays an important role in industry. Here we developed a novel redox-responsive surfactant, 3-(11-benzylselanyl-undecyl)-dimethylammonium acetate (BSeUCB), using selenium atoms as an environmentally sensitive group. In a reduced state, BSeUCB aqueous solution showed good foaming and emulsification abilities as well as conventional betaine surfactants. After oxidization, BSeUCB transformed into a bola-type structure because of the presence of a new hydrophilic group (selenoxide), and thus the critical micellar concentration, equilibrium surface/interfacial tension, and molecular area at the interface correspondingly increase from 0.32 mM, 46.43 mN·m(-1), 5.30 mN·m(-1), and 0.61 nm(2) to 4.98 mM, 59.15 mN·m(-1), 18.29 mN·m(-1), and 1.22 nm(2), respectively, resulting in a greater amount of energy input required to produce foam or emulsion, and a less dense adsorption layer, i.e., poor foaming and emulsification ability. Such a conversion was reversibly controlled by simply adding a trace amount (<0.06 wt % of the dispersion) of oxidant (H2O2) and reductant (Na2SO3). The products of the redox reaction did not interfere in the switchability except at the first cycle. The oxidization was generally time-consuming, whereas the reduction was very fast.

Fatty acid soaps such as sodium stearate (NaOSA) represent a class of cheap, environmentally friendly surfactants; however, their poor solubility seriously challenges their application in various fields. Herein, we describe a CO2/pH-controllable viscoelastic nanostructured fluid, which was developed by simple mixing of the commodity soap NaOSA with a bola-type quaternary ammonium salt (Bola2be) in a 2:1 molar ratio without the need for complex organic synthesis. The introduction of Bola2be increased NaOSA solubility and promoted micelle growth by forming a noncovalent pseudo-Gemini structure, 2NaOSA-Bola2be. Long aggregates are formed with increases in concentration, and these become entangled into a three-dimensional network at 10 times that of the critical micelle concentration (0.057 mM), showing strong thickening ability. Micellar branching occurs above 22.38 mM, as deduced by rheology and verified by cryo-transmission electron microscopy. The worm-based fluid formed from the noncovalent pseudo-Gemini surfactant is highly thermosensitive, and features a higher flow activation energy of 399.76 kJ·mol(-1) compared with common worm systems. Because of the pH-sensitivity of NaOSA, the viscoelastic fluid can respond to common pH stimuli or green CO2 gas, and shows a transition between a gel-like wormlike micellar network and a water-like dispersion with precipitate. However, the CO2-responsive behavior is irreversible.

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