Nanogels and Microgels: From Model Colloids to Applications, Recent Developments, and Future Trends.

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.

Sphere-Tubule Superstructures through Supramolecular and Supracolloidal Assembly Pathways.

While colloids have been widely employed as models for atoms and molecules, the current study proposes to extend their use as building blocks for supracolloidal frameworks. Hereby, the self-assembly between highly anisotropic supramolecular microtubules and soft spherical fluorescent microgels is explored using confocal laser scanning microscopy. The influence of the particle size and charge with respect to the catanionic tubule composition, which consists of two oppositely charged bile salt derivatives, is investigated. Under certain conditions, microgel particles are found to specifically interact with the extremities of the tubular aggregates and hierarchically self-assemble into various superstructures varying from virus-like assemblies to supracolloidal networks. The reported approach is envisioned to open new self-assembly routes toward ordered hybrid superstructures where the spherical colloids act as responsive linkers of tubular structures.

Quantitative analysis of polymer colloids by cryo-transmission electron microscopy.

The structure of colloidal latex particles in dilute suspension at room temperature is investigated by cryogenic transmission electron microscopy (cryo-TEM). Two types of particles are analyzed: (i) core particles made of polystyrene with a thin layer of poly(N-isopropylacrylamide) (PNIPAM) and (ii) core-shell particles consisting of core particles onto which a network of cross-linked PNIPAM is affixed. Both systems are also studied by small-angle X-ray scattering (SAXS). The radial density profile of both types of particles have been derived from the cryo-TEM micrographs by image processing and compared to the results obtained by SAXS. Full agreement is found for the core particles. There is a discrepancy between the two methods in case of the core-shell particles. The discrepancy is due to the buckling of the network affixed to the surface. The buckling is clearly visible in the cryo-TEM pictures. The overall dimensions derived from cryo-TEM agree well with the hydrodynamic radius of the particles. The comparison of these data with the analysis by SAXS shows that SAXS is only sensitive to the average radial structure as expected. All data show that cryo-TEM micrographs can be evaluated to yield quantitative information about the structure of colloidal particles.

Shear stresses of colloidal dispersions at the glass transition in equilibrium and in flow.

We consider a model dense colloidal dispersion at the glass transition, and investigate the connection between equilibrium stress fluctuations, seen in linear shear moduli, and the shear stresses under strong flow conditions far from equilibrium, viz., flow curves for finite shear rates. To this purpose, thermosensitive core-shell particles consisting of a polystyrene core and a cross-linked poly(N-isopropylacrylamide) shell were synthesized. Data over an extended range in shear rates and frequencies are compared to theoretical results from integrations through transients and mode coupling approaches. The connection between nonlinear rheology and glass transition is clarified. While the theoretical models semiquantitatively fit the data taken in fluid states and the predominant elastic response of glass, a yet unaccounted dissipative mechanism is identified in glassy states.

Thermosensitive core-shell particles as model systems for studying the flow behavior of concentrated colloidal dispersions.

We report on a comprehensive investigation of the flow behavior of colloidal thermosensitive core-shell particles at high densities. The particles consist of a solid core of poly(styrene) onto which a network of cross-linked poly(N-isopropylacrylamide) is affixed. Immersed in water the shell of these particles will swell if the temperature is low. Raising the temperature above 32 degrees C leads to a volume transition within this shell which leads to a marked shrinking of the shell. The particles have well-defined core-shell structure and a narrow size distribution. The remaining electrostatic interactions due to a small number of charges affixed to the core particles can be screened by adding 0.05M KCl to the suspensions. Below the lower critical solution temperature at 32 degrees C the particles are purely repulsive. Above this transition, a thermoreversible coagulation takes place. Lowering the temperature again leads to full dissociation of the aggregates formed by this process. The particles crystallize for effective volume fractions between 0.48 and 0.55. The crystallites can be molten by shear in order to reach a fluid sample again. The reduced shear stress measured in this metastable disordered state was found to be a unique function of the shear rate and the effective volume fraction. These reduced flow curves thus obtained can be described quantitatively by the theory of Fuchs and Cates [Phys. Rev. Lett. 89, 248304 (2002)] which is based on the mode-coupling theory of the glass transition.