Nanogels and microgels are soft, deformable and penetrable objects with an internal gel-like structure that is swollen by the dispersing solvent. Their softness and the potential to respond to external stimuli like temperature, pressure, pH, ionic strength and different analytes make them interesting as soft model systems in fundamental research as well as for a broad range of applications, in particular in the field of biological applications. Recent tremendous developments in their synthesis open access to systems with complex architectures and compositions allowing for tailoring microgels with specific properties. At the same time state-of-the-art theoretical and simulation approaches offer deeper understanding of the behavior and structure of nano- and microgels under external influences and confinement at interfaces or at high volume fractions. Developments in the experimental analysis of nano- and microgels have become particularly important for structural investigations covering a broad range of length scales relevant to the internal structure, the overall size and shape and inter-particle interactions in concentrated samples. Here we provide an overview of the state-of-the-art, recent developments as well as emerging trends in the field of nano- and microgels. The following aspects build the focus of our discussion: Tailoring (multi-)functionality through synthesis; the role in biological and biomedical applications; the structure and properties as model system, e.g. for densely packed arrangements in bulk and at interfaces; as well as the theory and computer simulation.
We propose a mean-field theory and dissipative particle dynamics (DPD) simulations of swelling and collapse of a polymer microgel adsorbed at the interface of two immiscible liquids (A and B). The microgel reveals surface activity and lowers A–B interfacial tension. Attempting to occupy as large an interfacial area as possible, the microgel undergoes anisotropic deformation and adopts a flattened shape. Spreading over the interface is restricted by polymer subchain elasticity. The equilibrium shape of the microgel at the interface depends on its size. Small microgels are shown to be more oblate than the larger microgels. Increasing microgel cross-link density results in stronger reduction of the surface tension and weaker flattening. As the degree of immiscibility of A and B liquids increases, the microgel volume changes in a non-monotonous fashion: the microgel contraction at moderate immiscibility of A and B liquids is followed by its swelling at high incompatibility of the liquids. The segregation regime of the liquids within and outside the microgel is different. Being segregated outside the microgel, the liquids can be fully (homogeneously) mixed or weakly segregated within it. The density profiles of the liquids and the polymer were plotted under different conditions. The theoretical and the DPD simulation results are in good agreement. We hope that our findings will be useful for the design of stimuli responsive emulsions, which are stabilized by the microgel particles, as well as for their practical applications, for instance, in biocatalysis.