IJMS, Vol. 20, Pages 6217: Polyelectrolyte-Nanoplatelet Complexation: Is It Possible to Predict the State Diagram? (International Journal of Molecular Sciences)

The addition of polyelectrolytes (PEs) to suspensions of charged colloids, such as nanoplatelets (NPs), is of great interest due to their specific feature of being either a stabilizing or a destabilizing agent. Here, the complexation between a PE and oppositely charged NPs is studied utilizing coarse-grained molecular dynamics simulations based on the continuum model. The complex formation is evaluated with respect to the stoichiometric charge-ratio within the system, as well as by the alternation of the chain properties. It is found that the formed complexes can possess either an extended or a compact shape. Moreover, it is observed that the chain can become overcharged by the oppositely charged NPs. With an increase in chain length, or a decrease in chain flexibility, the complex obtains a more extended shape, where the NPs are less tightly bound to the PE. The latter is also true when reducing the total charge of the chain by varying the linear charge density, whereas in this case, the chain contracts. With our coarse-grained model and molecular dynamics simulations, we are able to predict the composition and the shape of the formed complex and how it is affected by the characteristics of the chain. The take-home message is that the complexation between PEs and NPs results in a versatile and rich state diagram, which indeed is difficult to predict, and dependent on the properties of the chain and the model used. Thus, we propose that the present model can be a useful tool to achieve an understanding of the PE-NPs complexation, a system commonly used in industrial and in technological processes.