Molecular dynamics simulations of the interfacial and structural properties of dimethyldodecylamine-N-oxide micelles

A series of large-scale atomistic molecular dynamics simulations were conducted to study the structural and interfacial properties of nonionic dimethyldodecylamine-N-oxide (DDAO) micelles with an aggregation number of 104 in pure water, which was determined using small-angle neutron scattering (SANS). From these simulations, the micelles were found to be generally ellipsoidal in shape with axial ratios of ∼1.3-1.4, which agrees well with that found from small-angle neutron scattering measurements. The resulting micelles have an area per DDAO molecule of 94.8 Å(2) and an average number of hydration water molecules per DDAO molecule of ∼8. The effect of the encapsulation of ethyl butyrate (CH(3)(CH(2))(2)COOCH(2)CH(3), C(4)) and ethyl caprylate (CH(3)(CH(2))(6)COOCH(2)CH(3), C(8)) on the structural and interfacial properties of the nonionic DDAO aggregates was also examined. In the presence of the C(4) oil molecules, the aggregates were found to be less ellipsoidal and more spherical than the pure DDAO micelles, while the aggregates in the presence of the C(8) oil molecules were almost perfect spheres. In addition, the C(4) oil molecules move into the core of the aggregates, while the C(8) oil molecules stay in the headgroup region of the aggregates. Finally, the structural properties of two micelles formed from different starting states (a "preassembled" sphere and individual DDAO molecules distributing in water) were found to be nearly identical.