Surface Plasmons and Visible Light Iniferter Initiated Polymerization for Nanolocal Functionalization of Mesoporous Separation Layers

• Published in: Advanced functional materials Vol. 31; no. 20
• Main Authors: John, Daniel, Stanzel, Mathias, Andrieu‐Brunsen, Annette
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc 01.05.2021
• Subjects: Functional groups; Grafting; hybrid materials; Materials science; mesoporous silica thin films; Nanoalloys; Nanoparticles; Placement; plasmon induced polymerization; Plasmons; polymer functionalization; Polymerization; Polymers; Separation; Thickness; Thin films; visible light iniferter
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202009732

Although the technological relevance of mesoporous ceramic polymer hybrid materials is well accepted, missing functionalization concepts enabling 3D nanoscale local control of polymer placement into mesoporous materials, including thin films, and ideally using controlled polymerization techniques limit the application potential. Here, nanolocal functionalization of mesoporous separation layers using controlled, visible light iniferter initiated polymerization allowing responsive polymer functionalization locally limited to the irradiated spot is introduced. Thereby, two visible light sensitive iniferters, s‐p‐trimethoxysilylbenzyl‐S´‐dodecyltrithiocarbonate and 4‐cyano‐4‐((dodecylsulfanylthiocarbonyl)sulfanyl)pentanoic acid, are developed for polymer functionalization of mesoporous films in a grafting from and a grafting through approach. 3D nanolocal polymer placement close to the proximity of the plasmonic field source is demonstrated by combining these visible light iniferter initiated polymerizations with optical near field modes, such as localized surface plasmon resonance (LSPR). As the location of the LSPR in mesoporous films can be controlled by placing metal alloy nanoparticles into these films and film thicknesses can be adjusted, this strategy is applied for precise positioning of polymers into mesoporous films with nanolocal control in three dimensions and thus reduces the gap in precision of functional group positioning between technological and biological nanopores. Polymer functionalization of mesoporous separation layers with 3D nanolocal control is demonstrated by applying visible light and near field induced iniferter initiated polymerization. Two visible light sensitive iniferters are investigated in grafting through as well as grafting from approaches. Nanolocal polymer functionalization is achieved by applying gold‐silver alloy nanoparticles as the nanoscopic light source located inside the mesoporous separation layers.