Molecular dynamics simulations of structure-property relationships of Tween 80 surfactants in water and at interfaces

We build a united atom model for Tween 80 (polyoxyethylene sorbitan oleates), based on the GROMOS53A6(OXY+D) force field, and apply it to two stereoisomers, three constitutional isomers, and three structures with one, two, and three tails, to represent components in the Tween 80 commercial mixture. In a preassembled micelle containing 60 molecules, the distribution of Tween tail and ethylene oxide head groups is found to be insensitive to stereoisomerization but sensitive to changes in relative lengths of the four polyoxyethylene head groups. At the air-water and oil-water interfaces, the interfacial tension is significantly lower for the constitutional isomer with a shorter W headgroup, which attaches the tail to the sorbitan ring, and for Tween 80 isomers with more than one tail group. The results indicate the possible scope for improvement in the design of polyoxyethylene sorbitan oleates with improved surface tension reduction or better spreading at the oil-water interface. We also report surfactant component distribution profiles within preassembled micelles and at interfaces that can be used for validating coarse-grained surfactant models needed for simulation of self-assembly of Tween 80 surfactant mixtures.