In Situ Surface-Initiated ATRP Mediated by Gallium-Based Liquid Metal Nanodroplets.

Surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most popular methods for surface modifications with functional polymer films, which has attracted significant attention in recent years. Herein, a facile method of gallium-based liquid metal (GLM) nanodroplets mediated SI-ATRP to prepare polymer brushes on GLM surfaces is reported. The ATRP initiator modified GLM (GLM-Br) nanodroplets act as a substrate for the in situ SI-ATRP and participate as a reducing agent to reduce Cu(II) deactivators to Cu(I) activators. UV-vis spectra confirm the feasibility of the in situ SI-ATRP and indicate that the thickness and density of polymer brushes play an important role in performing a successful ATRP on GLM nanodroplets surfaces. Homo- and block copolymers, poly(3-sulfopropyl methacrylate potassium salt) (PSPMA) and poly((2-dimethylamino)ethyl methacrylate-b-(3-sulfopropyl methacrylate potassium salt)) P(DMAEMA-b-SPMA) are successfully grafted to the GLM nanodroplets. Polymer brushes modified GLM nanodroplets show potential applications such as friction reduction and oil-water emulsion separation. GLM nanodroplets mediated SI-ATRP provides a novel and robust approach to preparing multifunctional GLM nanodroplets for different applications.

Grafting Robust Thick Zwitterionic Polymer Brushes via Subsurface-Initiated Ring-Opening Metathesis Polymerization for Antimicrobial and Anti-Biofouling.

In the present work, high-thickness zwitterionic polymer brushes based on imidazolium salts were successfully grafted via a novel subsurface-initiated ring-opening metathesis polymerization (subsurface-initiated ROMP) from polydimethylsiloxane (PDMS), and their antifouling performance was evaluated in detail. First, an initiator-embedded PDMS was prepared via copolymerization of PDMS prepolymer and ROMP initiator, and then zwitterionic polymer brushes were grafted via subsurface-initiated ROMP from surface to subsurface of the PDMS due to the implanted ROMP initiator. Results from a series of characterization methods such as infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle, and atomic force microscopy proved the zwitterionic polymer brushes' successful grafting. The grafting thickness of zwitterionic polymer brushes via subsurface-initiated ROMP can reach the micron scale, and the as-prepared zwitterionic polymer based surfaces showed good lubricating properties compared to traditional surface-initiated ROMP, which hints that polymer brushes can be grafted not only on the surface but also on the subsurface of PDMS. The protein adhesion test and biofouling assay of zwitterionic polymer brushes were tested in the laboratory, and the results indicated that the zwitterionic polymer-functionalized PDMS can effectively resist the adhesion of bovine serum albumin and algae (Porphyridium and Dunaliella) and has good anti-bacterial activity against both Escherichia coli and Staphylococcus aureus.