Modulation of the deswelling temperature of thermoresponsive microgel films.

We demonstrate fine-tuning of the deswelling temperatures of thermoresponsive microgels within a biologically relevant range (30-40 °C). This was achieved by copolymerizing N-isopropylacrylamide and N-isopropylmethacrylamide (NIPAm and NIPMAm, respectively) in varying ratios; the parent homopolymers are well-known thermoresponsive polymers. Polyelectrolyte layer-by-layer (LbL) assemblies of these microgels retain the temperature response properties as demonstrated by temperature-dependent light scattering. Furthermore, films composed of more than one type of microgel building block were shown to have multiple temperature responses similar to those observed for the individual building blocks, permitting further tailoring of the temperature responsive interface. Additional experiments with mixed composition films, investigating multiple assembly processes, show that the location of the microgels within the film does not interfere with the temperature response. This suggests that microgels within the polyelectrolyte assembly behave independently of neighboring microgels with respect to their thermally induced deswelling.