We investigate the influence of a solid core and of the cross-link density on the compression of microgel particles at oil-water interfaces by means of compression isotherms and computer simulations. We investigate particles with different morphology, namely core-shell particles containing a solid silica core surrounded by a cross-linked polymer shell of poly(N-isopropylacrylamide), and the corresponding hollow microgels where the core was dissolved. The polymer shell contains different amounts of cross-linker. The compression isotherms show that the removal of the core leads to an increase of the surface pressure at low compression, and the same effect can be observed when the polymer cross-link density is decreased. Low cross-link density and a missing core thus facilitate spreading of the polymer chains at the interface and, at high compression, hinder the transition to close hexagonal packing. Furthermore, the compression modulus only depends on the cross-link density at low compression, and no difference can be observed between the core-shell particles and the corresponding hollow microgels. It is especially remarkable that a low cross-link density leads to a high compression modulus at low compression, while this behavior is reversed at high compression. Thus, the core does not influence the particle behavior until the polymer shell is highly compressed and the core is directly exposed to the pressure. This is related to an enhanced spreading of polymer chains at the interface and thus high adsorption energy. These conclusions are fully supported by computer simulations which show that the cross-link density of the polymer shell defines the degree of deformation at the interface. Additionally, the core restricts the spreading of polymer chains at the interface. These results illustrate the special behavior of soft microgels at liquid interfaces.

We report on hollow shell-shell nanogels with two polymer shells that have different volume phase transition temperatures. By means of small angle neutron scattering (SANS) employing contrast variation and molecular dynamics (MD) simulations we show that hollow shell-shell nanocontainers are ideal systems for controlled drug delivery: The temperature responsive swelling of the inner shell controls the uptake and release, while the thermoresponsive swelling of the outer shell controls the size of the void and the colloidal stability. At temperatures between 32 °C < T < 42 °C, the hollow nanocontainers provide a significant void, which is even larger than the initial core size of the template, and they possess a high colloidal stability due to the steric stabilization of the swollen outer shell. Computer simulations showed, that temperature induced switching of the permeability of the inner shell allows for the encapsulation in and release of molecules from the cavity.

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.