Reactive films fabricated using click sulfur(vi)–fluoride exchange reactions via layer-by-layer assembly

Abstract

The fabrication of multilayer assemblies from polymeric compounds is an important tool for meeting the increasing demand in functional surface-based research areas. In this report, a novel and efficient approach for the fabrication of polymer multilayered films using the “sulfur(VI)–fluoride exchange” (SuFEx) click reaction is described. To develop this approach, a sulfonyl fluoride-rich polymer, poly(N-vinyl-2-pyrrolidone)-co-poly(3-(fluorosulfonyl)-propyl methacrylate) (PVP-co-PFPM), and a silyl ether-rich polymer, tert-butyldimethylsilyl-modified polyvinyl alcohol (PVA-TBDMS), were chosen as model polymers. Through step-and-repeat spin-assisted layer-by-layer (LbL) procedures, multilayer films are then generated in which all the individual layers are covalently bonded to each other. Furthermore, multilayer films containing free sulfonyl fluoride groups can be readily functionalized via the SuFEx click reaction to tailor the properties of the films for various potential applications. As a proof-of-concept, using the (PVA-TBDMS/PVP-co-PFPM)₅ multilayer as a model film, the utility of the residual sulfonyl fluoride functionality for biomedical applications, such as H₂S biosensors and antibiofouling and antibacterial films, is demonstrated.