Controlling electrostatic co-assembly using ion-containing copolymers : from surfactants to nanoparticles

TL;DR

This review discusses how electrostatic interactions between charged-neutral diblock copolymers and nanocolloids like surfactants and nanoparticles can be controlled to form hierarchical structures with potential applications in designing functional supracolloidal assemblies.

Contribution

It introduces new protocols for controlling electrostatic co-assembly and demonstrates the formation of stable, functional nanostructures using ion-containing copolymers and inorganic nanoparticles.

Findings

Hierarchical core-shell structures form spontaneously above a critical charge ratio.

Desalting kinetics can be monitored to control assembly processes.

Stable, superparamagnetic aggregates with enhanced functionalities are achieved.

Abstract

In this review, we address the issue of the electrostatic complexation between charged-neutral diblock copolymers and oppositely charged nanocolloids. We show that nanocolloids such as surfactant micelles and iron oxide magnetic nanoparticles share similar properties when mixed with charged-neutral diblocks. Above a critical charge ratio, core-shell hierarchical structures form spontaneously under direct mixing conditions. The core-shell structures are identified by a combination of small-angle scattering techniques and transmission electron microscopy. The formation of multi-level objects is driven by the electrostatic attraction between opposite charges and by the release of the condensed counterions. Alternative mixing processes inspired from molecular biology are also described. The protocols applied here consist in screening the electrostatic interactions of the mixed dispersions, and then removing the salt progressively as example by dialysis. With these techniques, the oppositely charged species are intimately mixed before they can interact, and their association is monitored by the desalting kinetics. As a result, sphere- and rod-like aggregates with remarkable superparamagnetic and stability properties are obtained. These findings are discussed in the light of a new paradigm which deals with the possibility to use inorganic nanoparticles as building blocks for the design and fabrication of supracolloidal assemblies with enhanced functionalities.