A microgel-Pickering emulsion route to colloidal molecules with temperature-tunable interaction sites

A simple Pickering emulsion route has been developed for the assembly of temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) microgel particles into colloidal molecules comprising a small number of discrete microgel interaction sites on a central oil emulsion droplet. Here, the surface activity of the microgels serves to drive their assembly through adsorption to growing polydimethylsiloxane (PDMS) emulsion oil droplets of high monodispersity, prepared in situ via ammonia-catalysed hydrolysis and condensation of dimethyldiethoxysilane (DMDES). A dialysis step is employed in order to limit further growth once the target assembly size has been reached, thus yielding narrowly size-distributed, colloidal molecule-like microgel-Pickering emulsion oil droplets with well-defined microgel interaction sites. The temperature-responsiveness of the PNIPAM interaction sites will allow for the directional interactions to be tuned in a facile manner with temperature, all the way from soft repulsive to short-range attractive as the their volume phase transition temperature (VPTT) is crossed. Finally, the microgel-Pickering emulsion approach is extended to a mixture of PNIPAM and poly(N-isopropylmethacrylamide) (PNIPMAM) microgels that differ with respect to their VPTT, this in order to prepare patchy colloidal molecules where the directional interactions will be more readily resolved.