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 interparticle 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 a model system, e.g., for densely packed arrangements in bulk and at interfaces; as well as the theory and computer simulation.

We investigate soft, temperature-sensitive microgels at fluid interfaces. Though having an isotropic, spherical shape in bulk solution, the microgels become anisotropic upon adsorption. The structure of microgels at interfaces is described by a core−corona morphology. Here, we investigate how changing temperature across the microgel volume phase transition temperature, which leads to swelling/ deswelling of the microgels in the aqueous phase, affects the phase behavior within the monolayer. We combine compression isotherms, atomic force microscopy imaging, multiwavelength ellipsometry, and computer simulations. At low compression, the interaction between adsorbed microgels is dominated by their highly stretched corona and the phase behavior of the microgel monolayers is the same. The polymer segments within the interface lose their temperature-sensitivity because of the strong adsorption to the interface. At high compression, however, the portions of the microgels that are located in the aqueous side of the interface become relevant and prevail in the microgel interactions. These portions are able to collapse and, consequently, the isostructural phase transition is altered. Thus, the temperature-dependent swelling perpendicular to the interface ("3D") affects the compressibility parallel to the interface ("2D"). Our results highlight the distinctly different behavior of soft, stimuli-sensitive microgels as compared to rigid nanoparticles.

This work concerns interfacial adsorption and attachment of swollen microgel with low- to medium-level cross-linking density. Compared to colloids that form a second, dispersed phase, the suspended swollen microgel particles are ultrahigh molecular weight molecules, which are dissolved like a linear polymer, so that solvent and solute constitute only one phase. In contrast to recent literature in which microgels are treated as particles with a distinct surface, we consider solvent-solute interaction as well as interfacial adsorption based on the chain segments that can form trains of adsorbed segments and loops protruding from the surface into the solvent. We point out experimental results that support this discrimination between particles and microgels. The time needed for swollen microgels to adsorb at the air/water interface can be 3 orders of magnitude shorter than that for dispersed particles and decreases with decreasing cross-linking density. Detailed analysis of the microgels deformation, in the dry state, at a solid surface enabled discrimination particle like microgel in which case spreading was controlled predominantly by the elasticity and molecule like adsorption characterized by a significant overstreching, ultimately leading to chain scission of microgel strands. Dissipative particle dynamics simulations confirms the experimental findings on the interfacial activity and spreading of microgel at liquid/air interface.