Recently, it has been proposed that organic aerosol particles in the atmosphere can exist in an amorphous semi-solid or solid (i.e. glassy) state. In this perspective, we analyse and discuss the formation and properties of amorphous semi-solids and glasses from organic liquids. Based on a systematic survey of a wide range of organic compounds, we present estimates for the glass forming properties of atmospheric secondary organic aerosol (SOA). In particular we investigate the dependence of the glass transition temperature T(g) upon various molecular properties such as the compounds' melting temperature, their molar mass, and their atomic oxygen-to-carbon ratios (O:C ratios). Also the effects of mixing different compounds and the effects of hygroscopic water uptake depending on ambient relative humidity are investigated. In addition to the effects of temperature, we suggest that molar mass and water content are much more important than the O:C ratio for characterizing whether an organic aerosol particle is in a liquid, semi-solid, or glassy state. Moreover, we show how the viscosity in liquid, semi-solid and glassy states affect the diffusivity of those molecules constituting the organic matrix as well as that of guest molecules such as water or oxidants, and we discuss the implications for atmospheric multi-phase processes. Finally, we assess the current state of knowledge and the level of scientific understanding, and we propose avenues for future studies to resolve existing uncertainties.

Cultivation of adherently growing cells in artificial environments is of utmost importance in medicine and biotechnology to accomplish in vitro drug screening or to investigate disease mechanisms. Precise cell manipulation, like localized control over adhesion, is required to expand cells, to establish cell models for novel therapies and to perform noninvasive cell experiments. To this end, we developed a method of gentle, local lift-off of mammalian cells using polymer surfaces, which are reversibly and repeatedly switchable between a cell-attractive and a cell-repellent state. This property was introduced through micropatterned thermoresponsive polymer coatings formed from colloidal microgels. Patterning was obtained through automated nanodispensing or microcontact printing, making use of unspecific electrostatic interactions between microgels and substrates. This process is much more robust against ambient conditions than covalent coupling, thus lending itself to up-scaling. As an example, wound healing assays were accomplished at 37 °C with highly increased precision in microfluidic environments.

Abstract:In this work, we compare the properties of smart homopolymer microgels based on N-n-propylacrylamide (NNPAM), N-isopropylacrylamide (NIPAM) and N-isopropylmethacrylamide (NIPMAM) synthesized under identical conditions. The particles are studied with respect to size, morphology, and swelling behavior using scanning electron and scanning force microscopy. In addition, light scattering techniques and fluorescent probes are employed to follow the swelling/de-swelling of the particles. Significant differences are found and discussed. Poly(N-n-propylacrylamide) (PNNPAM) microgels stand out due to their very sharp volume phase transition, whereas Poly(N-isopropylmethacrylamide) (PNIPMAM) particles are found to exhibit a more homogeneous network structure compared to the other two systems.

Abstract:For the effective use of live cells in biomedicine as in vitro test systems or in biotechnology, non-invasive cell processing and characterisation are key elements. Thermoresponsive polymer coatings have been demonstrated to be highly beneficial for controlling the interaction of adherent cells through their cultivation support. However, the widespread application of these coatings is hampered by limitations in their adaptability to different cell types and because the full range of applications has not yet been fully explored. In the work presented here, we address these issues by focusing on three different aspects. With regard to the first aspect, by using well-defined laminar flow in a microchannel, a highly controllable and reproducible shear force can be applied to adherent cells. Employing this tool, we demonstrate that cells can be non-invasively detached from a support using a defined shear flow. The second aspect relates to the recent development of simple methods for patterning thermoresponsive coatings. Here, we show how such patterned coatings can be used for improving the handling and reliability of a wound-healing assay. Two pattern geometries are tested using mouse fibroblasts and CHO cells. In terms of the third aspect, the adhesiveness of cells depends on the cell type. Standard thermoresponsive coatings are not functional for all types of cells. By coadsorbing charged nanoparticles and thermoresponsive microgels, it is demonstrated that the adhesion and detachment behaviour of cells on such coatings can be modulated.

We investigated the influence of two anionic surfactants, namely, sodium dodecyl sulfate and sodium decyl sulfate, on acrylamide-based microgels consisting of N - n -propylacrylamide. In this context, the main focus was on the influence of surfactant addition on the size of the microgels. The surfactant was added to the reaction mixture before or during the polymerization at different points in time. Microgels were characterized via photon correlation spectroscopy and atomic force microscopy. All results were compared to those for other more common acrylamide-based microgels consisting of N- isopropylacrylamide and N -isopropylmethacrylamide. A significant difference between the three microgels and a strong dependence on the surface activity of the surfactant was found.