Microgels enable reversible stabilization of liquid crystal (LC) emulsions in ways that facilitate analysis of LC droplets that undergo an analyte-triggered conformational transition.
29 January 2024 in Angewandte Chemie International Edition
Water molecules play an important role in the structure, function, and dynamics of (bio‐) materials. A direct access to the number of water molecules in nanoscopic volumes can thus give new molecular insights into materials and allow for fine‐tuning their properties in sophisticated applications. The determination of the local water content has become possible by the finding that H2O quenches the fluorescence of red‐emitting dyes. Since deuterated water, D2O, does not induce significant fluorescence quenching, fluorescence lifetime measurements performed in different H2O/D2O‐ratios yield the local water concentration. We combined this effect with the recently developed fluorescence lifetime single molecule localization microscopy imaging (FL‐SMLM) in order to nanoscopically determine the local water content in microgels, i.e. soft hydrogel particles consisting of a cross‐linked polymer swollen in water. The change in water content of thermo‐responsive microgels when changing from their swollen state at room temperature to a collapsed state at elevated temperature could be analyzed. A clear decrease in water content was found that was, to our surprise, rather uniform throughout the entire microgel volume. Only a slightly higher water content around the dye was found in the periphery with respect to the center of the swollen microgels.
Microgels are deformable polymer-networks with conspicuous properties. Their surface- activity associated with their switchability makes their application in liquid-liquid systems, such as extraction processes, particularly promising. For their application as switchable stabilizers at the interface, a detailed understanding of their impact on process relevant phenomena, such as the sedimentation behavior, is necessary. So far, the focus of research has been on microscopic-scale properties, whereby the propagation to macroscopic effects has rarely been quantified. In this study, single microgel-covered n-butyl acetate drops rising in a quiescent continuous water phase are investigated experimentally. The dependency of the microgel properties, in terms of size and cross-linking density, on the fluid dynamics are addressed. The impact of microgels is studied in detail by sedimentation velocity, drop deformation and the resulting drag coefficient. The deformation of drops is related to shape conserving interfacial properties such as the interfacial tension. Counter to our expectations, microgel-covered drops deform less than the drops of the pure system although microgels reduce the interfacial tension. Moreover, the sedimentation velocity is of special interest, since it reveals the mobility of the interface and friction conditions at the interface. Our results demonstrate the correlation between microgel properties at the interface on a microscopic scale and the macroscopic behavior of microgel-covered drops.