ConspectusMicrogels 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 propert...

Functional Microgels and Microgel Systems

Smart drug delivery systems (DDSs) have attracted the attention of many scientists, as carriers that can be stimulated by changes in environmental parameters such as temperature, pH, light, electromagnetic fields, mechanical forces, etc. These smart nanocarriers can release their cargo on demand when their target is reached and the stimulus is applied. Using the techniques of nanotechnology, these nanocarriers can be tailored to be target-specific, and exhibit delayed or controlled release of drugs. Temperature-responsive nanocarriers are one of most important groups of smart nanoparticles (NPs) that have been investigated during the past decades. Temperature can either act as an external stimulus when heat is applied from the outside, or can be internal when pathological lesions have a naturally elevated termperature. A low critical solution temperature (LCST) is a special feature of some polymeric materials, and most of the temperature-responsive nanocarriers have been designed based on this feature. In...

Temperature-Responsive Smart Nanocarriers for Delivery Of Therapeutic Agents: Applications and Recent Advances

Thermosensitive core–shell microgels: From colloidal model systems to nanoreactors

Recent studies revealing the unique properties of microgel-stabilized responsive emulsions are discussed, and microgels are compared to classical rigid-particle Pickering stabilizers. Microgels are strongly swollen, lyophilic particles that become deformed at the oil-water interface and protrude only a little into the oil phase. Temperature- and pH-sensitive microgels allow us to prepare temperature- and pH-sensitive emulsions and thus enable us to prepare and break emulsions on demand. Although such emulsions are sensitive to pH, the stabilization of droplets is not due to electrostatic repulsion, instead the viscoelastic properties of the interface seem to dominate droplet stability. Being soft and porous, microgels behave distinctly differently from rigid particles at the interface: they are deformed and strongly flattened especially in the case of oil-in-water emulsions. The microgels are located mainly on the water side of the interface for both oil-in-water and water-in-oil emulsions. In contrast to rigid, solid particles, the behavior of microgels at oil-water interfaces does not depend only on the interfacial tension but also on the balance among the interfacial tension, swelling, elasticity, and deformability of the microgel, which needs to be considered. It is obvious that microgels as soft, porous particles are significantly different from classical rigid colloidal stabilizers in Pickering emulsions and we suggest avoiding the term Pickering emulsion when swollen microgels are employed. Microgel-stabilized emulsions require the development of new theoretical models to understand their properties. They open the door to new sophisticated applications.

Responsive Emulsions Stabilized by Stimuli-Sensitive Microgels: Emulsions with Special Non-Pickering Properties

Emulsions stabilized by stimuli-responsive microgels were used to perform enzyme catalysis. Many substrates are poorly water-soluble, while enzymes naturally require aqueous environments, thus resulting in a two-phase aqueous-organic system. Smart microgels allow an enzyme-catalyzed reaction to be performed in an emulsion that can be broken under controlled conditions to separate the reaction product and to recycle the enzyme (E) and the microgel.

Microgel-Stabilized Smart Emulsions for Biocatalysis†

Two sets of core−shell microgels composed of temperature-sensitive poly(N-isopropylacrylamide) (PNiPAM) with different spatial distribution of pH-sensitive methacrylic acid (MAA) groups were prepared. The cores consist of either PNiPAM (neutral core; nc) or PNiPAM-co-MAA (charged core; cc). A charged shell existing of PNiPAM-co-MAA was added to the neutral core (yielding neutral core−charged shell; nccs), on the charged core, on the other hand, a neutral shell of PNiPAM was added (charged core−neutral shell; ccns). Complexes of these microgels with positively charged poly(diallyldimethylammonium chloride) (PDADMAC) of different molar masses were prepared. The amount of bound polyelectrolyte was quantified, and the microgel−polyelectrolyte complexes were characterized with respect to electrophoretic mobility and hydrodynamic radius. The penetration of polyelectrolyte into the microgel was also monitored by means of lifetime analysis of a fluorescent dye covalently bound to poly(l-lysine) providing informat...

Influence of Architecture on the Interaction of Negatively Charged Multisensitive Poly(N-isopropylacrylamide)-co-Methacrylic Acid Microgels with Oppositely Charged Polyelectrolyte: Absorption vs Adsorption

Andreas Klee

Papers

Influence of Architecture on the Interaction of Negatively Charged Multisensitive Poly(N-isopropylacrylamide)-co-Methacrylic Acid Microgels with Oppositely Charged Polyelectrolyte: Absorption vs Adsorption