Cryo-electron tomography study of the evolution of wormlike micelles to saturated networks and perforated vesicles

[Display omitted] •Cryo-electron tomography was used to determine the structural characteristics of complicated surfactant aggregates.•Transitions branched WLMs → saturated network of WLMs → perforated vesicles were observed in solutions of zwitterionic and nonionic surfactants.•Transformations proceed through an increase in the number of branches at the expense of cylindrical subchains and semispherical endcaps.•Exponential distribution of subchains length was confirmed experimentally for multiconnected saturated networks.•Perforated vesicles were observed when the length of subchains became much shorter than the persistence length. The formation of micellar aggregates and the changes in their morphology are crucial for numerous practical applications of surfactants. However, a proper structural characterization of complicated micellar nanostructures remains a challenge. This paper demonstrates the advances of cryo-electron tomography (cryo-ET) in revealing the structural characteristics that accompany the evolution of surfactant aggregates. By using cryo-ET in combination with cryo-transmission electron microscopy (cryo-TEM), small-angle neutron scattering (SANS), and rheometry, studies were carried out on a model system composed of zwitterionic and nonionic surfactants. In this system, the molecular packing parameter was increased gradually by increasing the molar fraction of nonionic surfactant. A series of structural transformations was observed: linear wormlike micelles (WLMs) → branched WLMs → saturated network of multiconnected WLMs → perforated vesicles (stomatosomes). The transformations occur through an increase in the number of branches at the expense of cylindrical subchains and semispherical endcaps. Exponential distribution of subchains length was confirmed experimentally for multiconnected saturated networks. The stomatosomes were formed when the length of subchains becomes much shorter than the persistence length, causing the three-dimensional (3D) structure to transform into a two-dimensional (2D) membrane. This work identifies the mechanism of the structural changes, which can be further used to design various surfactant self-assemblies.