Functional Microgels and Microgel Systems.

Microgels are macromolecular networks swollen by the solvent in which they are dissolved. They are unique systems that are distinctly different from common colloids, such as, e.g., rigid nanoparticles, flexible macromolecules, micelles, or vesicles. The size of the microgel networks is in the range of several micrometers down to nanometers (then sometimes called "nanogels"). In a collapsed state, they might resemble hard colloids but they can still contain significant amounts of solvent. When swollen, they are soft and have a fuzzy surface with dangling chains. The presence of cross-links provides structural integrity, in contrast to linear and (hyper)branched polymers. Obviously, the cross-linker content will allow control of whether microgels behave more "colloidal" or "macromolecular". The combination of being soft and porous while still having a stable structure through the cross-linked network allows for designing microgels that have the same total chemical composition, but different properties due to a different architecture. Microgels based, e.g., on two monomers but have either statistical spatial distribution, or a core-shell or hollow-two-shell morphology will display very different properties. Microgels provide the possibility to introduce chemical functionality at different positions. Combining architectural diversity and compartmentalization of reactive groups enables thus short-range coexistence of otherwise instable combinations of chemical reactivity. The open microgel structure is beneficial for uptake-release purposes of active substances. In addition, the openness allows site-selective integration of active functionalities like reactive groups, charges, or markers by postmodification processes. The unique ability of microgels to retain their colloidal stability and swelling degree both in water and in many organic solvents allows use of different chemistries for the modification of microgel structure. The capability of microgels to adjust both their shape and volume in response to external stimuli (e.g., temperature, ionic strength and composition, pH, electrochemical stimulus, pressure, light) provides the opportunity to reversibly tune their physicochemical properties. From a physics point of view, microgels are particularly intriguing and challenging, since their intraparticle properties are intimately linked to their interparticle behavior. Microgels, which reveal interface activity without necessarily being amphiphilic, develop even more complex behavior when located at fluid or solid interfaces: the sensitivity of microgels to various stimuli allows, e.g., the modulation of emulsion stability, adhesion, sensing, and filtration. Hence, we envision an ever-increasing relevance of microgels in these fields including biomedicine and process technology. In sum, microgels unite properties of very different classes of materials. Microgels can be based on very different (bio)macromolecules such as, e.g., polysaccharides, peptides, or DNA, as well as on synthetic polymers. This Account focuses on synthetic microgels (mainly based on acrylamides); however, the general, fundamental features of microgels are independent of the chemical nature of the building moieties. Microgels allow combining features of chemical functionality, structural integrity, macromolecular architecture, adaptivity, permeability, and deformability in a unique way to include the "best" of the colloidal, polymeric, and surfactant worlds. This will open the door for novel applications in very different fields such as, e.g., in sensors, catalysis, and separation technology.