Dissipative particle dynamics simulations on inversion dynamics of spherical micelles

Abstract

We simulate the inversion process of a spherical micelle composed of symmetric diblock copolymers by means of dissipative particle dynamics. The evolution of micelle morphology reveals that the inversion is a two-staged process, in which a rapid agglomeration of outer lyophobic blocks occurs first, followed by a slow penetration of inner lyophilic blocks through the porous lyophobic layer. Calculation of the radius of gyration and hydrodynamic radius indicates that an intermediate with a dilute core and a dense shell emerges in the inversion. The characteristic time of inversion scales with the block copolymer chain length with the scaling exponent ranging from 1.67 to 1.89, which can be well described by a simplified chemical-potential-driven flow model. Further simulations incorporating different denaturation times for the two types of blocks indicate the inversions do not experience molecularly scattered states, but form either collapsed intermediates or loosely associated clusters of small sizes. Possible connections of the simulations to the light scattering experiments are discussed.