Scission energy and topology of micelles controlled by the molecular structure of additives

Abstract

We employ coarse-grained (CG) molecular dynamics simulations (MD) to investigate the effects of the molecular structure of additives on the scission energy and morphology of charged micelles. Considering sodium dodecyl sulfate (SDS) as a representative charged surfactant and taking trimethylphenylammonium chloride (TMPAC) and octyltrimethylammonium bromide (OTAB) as oppositely charged additives, we show that the scission energy and topology of micelles vary significantly depending on the molecular structure of the hydrophobic part of the additives. The cyclic aromatic tail of the TMPAC disrupts the core structure of the SDS micelle and hence decreases the micelle scission energy, whereas the linear alkyl tail of the OTAB packs very well with the micelle core and increases the scission energy. Although both the additives have similar head structures, they lead to very different micelle morphologies because of the difference in the shape of their tail structures; ring-like or toroidal shaped micelles are formed in SDS/TMPAC solution whereas bicelle-like structures are formed in SDS/OTAB solution when the additive to surfactant ratio is higher than a certain value.