Layer-selective functionalisation in mesoporous double layer via iniferter initiated polymerisation for nanoscale step gradient formation

Functionalisation of technological nanopores and investigation of their transport properties have attracted considerable interest from scientific as from technological point of view, among others due to their potential regarding molecular transport design. Asymmetric design of nanopore structure and functionalisation is expected to trigger increased and directed transport of ionic species. Based on this motivation, we demonstrate a layerselective polymer functionalisation in a mesoporous double layer thin film to generate nanoscale step gradient architectures with asymmetric charge distribution by taking advantage of co-condensation and polymer modification techniques. Thereby, mesoporous silica and co-condensed mesoporous amino silica thin films are combined to double layered films with a film thickness of 300 - 400 nm in both sequential arrangements, respectively. Iniferter initiated polymerisation is used to selectively functionalise only the amino silica layer with polymers such as poly(2-(methacryloyloxy)ethyltrimethylammonium chloride) (PMETAC) in a grafting from approach. Investigation of the ionic pore accessibility of the mesoporous double layered films before and after layer-selective polymer functionalisation shows that the ionic pore accessibility is dominated by the bottom layer when overcoming the electrostatic repulsion of the top layer.