Impact of Copolymer Architecture on Demicellization and Cargo Release via Head-to-Tail Depolymerization of Hydrophobic Blocks or Branches.

Utilizing molecular dynamics simulations, we explored the demicellization and cargo release dynamics of linear and miktoarm copolymers, featuring one, two, and three hydrophobic blocks or branches, each capable of head-to-tail depolymerization. Our findings revealed that, under stoichiometric trigger molecule concentrations, miktoarms with three branches exhibited consistently faster depolymerization rates than those with two branches and linear copolymers. Conversely, at constant trigger molecule concentrations, the depolymerization rates of copolymers exhibited more complex behaviors influenced by two opposing factors: the excess of trigger molecules, which increased with a decrease in the number of hydrophobic branches or blocks, and simultaneous head-to-tail depolymerization, which intensified with an increasing number of branches.

Chemical Feedback in Templated Reaction-Assembly of Polyelectrolyte Complex Micelles: A Molecular Simulation Study of the Kinetics and Clustering.

The chemical feedback between building blocks in templated polymerization of diblock copolymers and their consecutive micellization was studied for the first time by means of coarse-grained molecular dynamics simulations. Using a stochastic polymerization model, we were able to reproduce the experimental findings on the effect of chemical feedback on the polymerization rates at low and high solution concentrations. The size and shape of micelles were computed using a newly developed software in Python conjugated with graph theory.