Simulation Analysis of the Kinetic Exchange of Copolymer Surfactants in Micelles

The exchange of surfactants in micelles involves several processes that are difficult to characterize experimentally. Microscopic simulations have the potential to reveal some of the key activities that occur when a surfactant spontaneously exits a micelle. In this work, we present a quantitative analysis of the kinetic exchange process over a large range of time. This study is based on a dynamic version of single-chain mean-field theory using a coarse-grained model for poly(ethylene oxide)poly(propylene oxide)poly(ethylene oxide) triblock copolymer systems. The kinetics described in our simulations involves three different regimes. After a fast initial rearrangement of the labeled chains, the system undergoes a logarithmic relaxation, which has been experimentally observed. Contrary to what has been reported in previous analyses, our simulations indicate that this regime is caused by the intrinsic physical behavior of the system and is not due only to the polydispersity of the samples. Finally, the terminal regime is characterized by an exponential decay. The exit rates predicted by our simulations are in good agreement with the values reported experimentally. In addition, we address the sequence of microscopic conformational changes undergone by the surfactants when leaving the micellar aggregates. We found a subtle variation in the radius of gyration of the hydrophobic block, which challenges the image of either a complete collapse or a full stretching commonly accepted in the current theoretical and experimental literature.