The structural and electrical characteristics of polyelectrolyte complex micelles (PCMs) formed by mixing of oppositely charged double hydrophilic copolymers are studied by means of molecular dynamics simulations. In mixtures of linear diblock copolymers we found that the preferential aggregation numberNpof PCMs is a universal function of the ratioγ±of the total positive to total negative charges of the mixture. The addition of divalent salts ions induces a secondary micellization. In mixtures of copolymers bearing a common neutral thermoresponsive block, micelles with contracted corona consisting of thermoresponsive blocks and complex polyelectrolyte core are formed at low salt concentration and temperature far away the biphasic regime. At high salt concentration and temperature in the biphasic regime, reversed micelles are obtained. In equimolar mixtures of linear copolymers with miktoarm stars we found thatNpof PCMs decreases as the number of charged branches of miktoarm copolymer increases. The shape of micelles progressively changes from spherical to worm‐like with the increase of number of branches of miktoarm copolymers. Our findings are in full agreement with existing experimental and theoretical predictions and provides new and additional insights.

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 development software in python conjugated with graph theory. In full agreement with the experiments, our simulations revealed that micelles formed by the templated micellization are more spherical and have lower radius of gyration than those formed by the traditional two-step micellization method. Understanding the underlying mechanisms in templated reaction/assembly of polymers will help for rational design of new synthetic supramolecular materials.

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. In full agreement with the experiments, our simulations revealed that micelles formed by the templated micellization are more spherical and have a lower radius of gyration than those formed by the traditional two-step micellization method. The advantage of molecular simulation over the traditional kinetic models is that with the simulation, one studies in detail the heterogeneous polymerization in the presence of the oppositely charged template while also accounting for the incompatibility between reacted species, which significantly influences the reaction process.

The internal stratification of a polyelectrolyte complex (zipper brush) formed by mixing of an anionic charged polyelectrolyte brush (PEB) with cationic-neutral diblock copolymers bearing a very long neutral block is studied by means of molecular dynamics simulations. The authors find that the fraction of the neutralized PEB units in the mixture increases as the fraction of the PEB charged units (a) increase for high grafting densities (d). Due to the charge neutralization condition, from the initial PEB through the complexation with the appropriate choice of a cationic-neutral copolymer, neutral brush having grafting density lower, equal, or much higher than that of the PEB are obtained. The addition of monovalent salt in the mixture with concentrations 0.1 and 1 m leads to a reduction in complexed diblock copolymer chains of up to 91% and practically the initial PEB is recovered. The findings are in full agreement with existing experimental predictions and provide new insights into the structure and the shape of the coacervate. The latter progressively changes from a dense film to perforated film, to lamella, to pinned micelles, to stacks as a, d, and the molecular weights of the PEB and diblock copolymer blocks are altered.