Ion-specific effects widely exist in biological and chemical systems and cannot be explained by classical theories. The complexity of ion-specific effects in protein systems at the molecular level necessitates the use of mimetic models involving smaller molecules, such as amino acids, oligopeptides, and other organic molecules bearing amide bonds. Therefore, it is of theoretical value to determine the effect of additional salts on the aggregation transitions of acyl amino acid surfactants. Herein, the effects of specific tetraalkylammonium ions (TAA+) on sodium lauroyl glycinate (SLG) aggregation were studied by dynamic light scattering (DLS) and transmission electron microscopy. Although previous studies have shown that the kosmotropic TAA+ ions tend to induce micellar growth or micelle-to-vesicle transitions of some anionic surfactants, TAA+ addition in the present study induced partial vesicle-to-micelle transitions in SLG solutions. The chemical trapping (CT) method was employed to estimate changes in the interfacial molarities of water, amide bonds, and carboxylate groups during such transitions. The vesicle-to-micelle transitions were accompanied by a marked rise in interfacial water molarity and a decline in interfacial amide bonds molarity, suggesting that the hydrated TAA+ entered the interfacial region and disrupted hydrogen bonding, thus preventing the SLG monomers from packing tightly. Molecular dynamic simulation was also performed to demonstrate the salt-induced cleavage of amide–amide bonds between SLG headgroups. Furthermore, both CT and DLS results show that the ability of tetraalkylammonium cations to induce such transitions increased with increasing size and hydrophobicity of the cation, which follows the Hofmeister series. The current study offers critical molecular-level evidence for understanding the specific effects of tetraalkylammonium ions on the aggregation transitions of an acyl amino acid surfactant.

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In recent years, there has been increasing interest in daily-use chemical products providing a pleasant scent. The added fragrance molecules may induce microstructural transitions of surfactant aggregates, which further affect the physical and chemical properties of the products. Here, the effects of four types of aromatic alcohols (cinnamyl alcohol, phenyl ethanol, phenyl methanol and anisyl alcohol) on cetyltrimethylammonium bromide (CTAB)/KBr aggregates were studied. The combined results from rheology, dynamic light scattering, and transmission electron microscopy measurements showed that cinnamyl alcohol induced significant micellar growth, while increases in micellar growth were less obvious for the other aromatic alcohols. The changes in the interfacial molarities of water, aromatic alcohol, and bromide ions during such transitions were studied using the chemical trapping method. Transitions resulting from added cinnamyl alcohol were accompanied by significant declines in interfacial water and bromide ion molarities, and a rise in interfacial alcohol molarity. The marked decrease in interfacial water molarity was not observed in previous studies of the octanol induced formation of wormlike micelles and vesicles, indicating that a different mechanism was presented in the current system. Nuclear magnetic resonance investigation showed that π–π stacking between cinnamyl alcohols, but not cation–π interactions between alcohols and CTAB headgroups, facilitated the tight packing of alcohol molecules in CTAB aggregates and the repulsion of water from the interfacial region. The current study may provide a theoretical basis for the morphological regulation of surfactant aggregates in the presence of additives.

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Typically, the formation of vesicles requires the addition of salts or other additives to surfactant micelles. However, in the case of catanionic surfactants, unilamellar vesicles can spontaneously form upon dilution of the micellar solutions. Our study explores the intriguing spontaneous vesicle-to-micelle transition in catanionic surfactant systems, specifically cetyltrimethyl ammonium bromide (CTAB) and sodium octylsulfonate (SOS). To gain insights into the changes occurring at the interface, we employ a chemical trapping method to characterize variations in the molarities of sulfonate headgroups, water, and bromide ions during the transition. Our findings reveal the formation of ion pairs between the cationic component of CTAB and the anionic component of SOS, leading to tight interfacial packing in CTAB/SOS solutions. This interfacial packing promotes vesicle formation at low surfactant concentrations. Due to the significant difference in critical micelle concentration (cmc) between CTAB and SOS, an increase in the stoichiometric surfactant concentration results in a substantial rise in the SOS-to-CTAB ratio within the interfacial region. This enrichment of SOS in the aggregates triggers the transition from vesicles to micelles. Overall, our study may shed new light on the design of morphologies in catanionic and other surfactant systems.