Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by ppm of CuII/Tris(2-pyridylmethyl)amine.

Atom transfer radical polymerization (ATRP) is one of the most widely used methods for modifying surfaces with functional polymer films and has received considerable attention in recent years. Here, we report an electrochemically mediated surface-initiated ATRP to graft polymer brushes onto solid substrates catalyzed by ppm amounts of CuII/TPMA in water/MeOH solution. We systematically investigated the type and concentrations of copper/ligand and applied potentials correlated to the polymerization kinetics and polymer brush thickness. Gradient polymer brushes and various types of polymer brushes are prepared. Block copolymerization of 2-hydroxyethyl methacrylate (HEMA) and 3-sulfopropyl methacrylate potassium salt (PSPMA) (poly(HEMA-b-SPMA)) with ultralow ppm eATRP indicates the remarkable preservation of chain end functionality and a pronounced "living" characteristic feature of ppm-level eATRP in aqueous solution for surface polymerization.

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.

Fabrication of Poly(ionic liquid) Hydrogels Incorporating Liquid Metal Microgels for Enhanced Synergistic Antifouling Applications.

Hydrogels are ideal for antifouling materials due to their high hydrophilicity and low adhesion properties. Herein, poly(ionic liquid) hydrogels integrated with zwitterionic copolymer-functionalized gallium-based liquid metal (PMPC-GLM) microgels were successfully prepared by a one-pot reaction. Poly(ionic liquid) hydrogels (IL-Gel) were obtained by chemical cross-linking the copolymer of ionic liquid, acrylic acid, and acrylamide, and the introduction of ionic liquid (IL) significantly increased the cross-linking density; this approach consequently enhanced the mechanical and antiswelling properties of the hydrogels. The swelling ratio of IL-Gel decreased eight times compared to the original hydrogels. PMPC-GLM microgels were prepared through grafting the zwitterionic polymer PMPC onto the GLM nanodroplet surface, which exhibited efficient antifouling performance attributed to the bactericidal effect of Ga3+ and the antibacterial effect of the zwitterionic polymer layer PMPC. Based on the synergistic effect of PMPC-GLM microgels and IL, the composite hydrogels PMPC-GLM@IL-Gel not only exhibited excellent mechanical and antiswelling properties but also showed outstanding antibacterial and antifouling properties. Consequently, PMPC-GLM@IL-Gel hydrogels achieved inhibition rates of over 90% against bacteria and more than 85% against microalgae.

Size-Regulated Metal-Organic Frameworks with Mercaptobenzothiazole for Ga-Based Liquid Metal Encapsulation: A High Performance Oil-Based Additive.

In this study, size-regulated MOFs (MZ) with high MBT loading were successfully synthesized by combining mercaptobenzothiazole (MBT), zinc salt, and 2-methylimidazole (2-MI). Subsequently, the MZ structure was utilized to encapsulate tannic acid-modified gallium-based liquid metal (GLM-TA), thereby acquiring a novel heterogeneous nanocomposite (GLM-TA@MZ). The results revealed that the as-prepared GLM-TA@MZ shows good antiwear and friction-reducing performance as an oil-based lubricant additive, the average friction coefficient was decreased to 0.091, and a wear volume was reduced to 0.95 × 104 µm3, which corresponds to a decrease of 52.3 and 97.2% as compared to base oil PAO. The excellent tribological properties of GLM-TA@MZ can be attributed to physical adsorption on the friction pair, followed by tribochemical reactions. As a result, a thick friction protection film (thickness of about 100 nm) containing Ga, Zn, and S elements was formed, which effectively reduced the contact area between the friction pairs, resulting in improved tribological performance. This study provides insights into the design of MOF-based nanocomposites for lubricating 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.