Vesicle formation of single-chain amphiphilic 4-dodecylbenzene sulfonic acid in water and micelle-to-vesicle transition induced by wet-dry cycles.

Simple single-chain amphiphiles (SCAs) can form vesicular structures in their single-component aqueous solutions, which has attracted great attention, but the understanding of their aggregation behavior is still limited. In this work, the aggregation behavior of 4-dodecylbenzene sulfonic acid (DBSA), a typical simple SCA, in water was investigated. The structure and properties of the aggregates formed were determined. In particular, the effect of wet-dry cycles on the structures of aggregates was examined. The mechanisms of aggregate formation and structural transition were discussed. It was found that the increase of DBSA concentration can drive the occurrence of a micelle-to-vesicle transition, showing a critical micelle concentration and critical vesicle concentration of ∼0.53 and 2.14 mM, respectively. The vesicles formed coexist with micelles in solution, with a unilamellar structure and ∼80 nm size, and exhibit size-selective permeability. In addition, the vesicles show remarkable stability upon long-term storage, exposure to high temperature, and freeze-thaw cycles. The H-bonding interaction between DBSA species and the interdigitated structure of alkyl chains in bilayers play a key role in the formation and stability of DBSA vesicles. Interestingly, it was found that the wet-dry cycle can induce a micelle-to-vesicle transition and an obvious increase in the size of the original vesicles, accompanied by the formation of some multilamellar vesicles. This work provides a better understanding of the aggregation behavior of simple SCAs in their single-component aqueous solutions.