ABSTRACT
The ability to tailor polymer brush coatings to the last nanometer has arguably placed them among the most powerful surface modification techniques currently available. Generally, the synthesis procedures for polymer brushes are designed for a specific surface type and monomer functionality and cannot be easily employed otherwise. Herein, we describe a modular and straightforward two-step grafting-to approach that allows introduction of polymer brushes of a desired functionality onto a large range of chemically different substrates. To illustrate the modularity of the procedure, gold, silicon oxide (SiO2), and polyester-coated glass substrates were modified with five different block copolymers. In short, the substrates were first modified with a universally applicable poly(dopamine) primer layer. Subsequently, a grafting-to reaction was performed on the poly(dopamine) films using five distinct block copolymers, all of which contained a short poly(glycidyl methacrylate) segment and longer segment of varying chemical functionality. Ellipsometry, X-ray photoelectron spectroscopy, and static water contact angle measurements confirmed successful grafting of all five block copolymers to the poly(dopamine)-modified gold, SiO2, and polyester-coated glass substrates. In addition, our method was used to provide direct access to binary brush coatings, by simultaneous grafting of two different polymer materials. The ability to synthesize binary brush coatings further adds to the versatility of our approach and paves the way toward production of novel multifunctional and responsive polymer coatings.
ABSTRACT
This work presents a novel route for creating metal-free antiviral coatings based on polymer brushes synthesized by surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization, applying eosin Y as a photocatalyst, water as a solvent, and visible light as a driving force. The polymer brushes were synthesized using N-[3-(decyldimethyl)-aminopropyl] methacrylamide bromide and carboxybetaine methacrylamide monomers. The chemical composition, thickness, roughness, and wettability of the resulting polymer brush coatings were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), water contact angle measurements, and ellipsometry. The antiviral properties of coatings were investigated by exposure to severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and avian influenza viruses, with further measurement of residual viable viral particles. The best performance was obtained with Cu surfaces, with a ca. 20-fold reduction of SARS-Cov-2 and a 50-fold reduction in avian influenza. On the polymer brush-modified surfaces, the number of viable virus particles decreased by about 5-6 times faster for avian flu and about 2-3 times faster for SARS-CoV-2, all compared to unmodified silicon surfaces. Interestingly, no significant differences were obtained between quaternary ammonium brushes and zwitterionic brushes.
ABSTRACT
This work presents a new method for the synthesis of antifouling polymer brushes using surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain-transfer polymerization with eosin Y and triethanolamine as catalysts. This method proceeds in an aqueous environment under atmospheric conditions without any prior degassing and without the use of heavy metal catalysts. The versatility of the method is shown by using three chemically different monomers: oligo(ethylene glycol) methacrylate, N-(2-hydroxypropyl)methacrylamide, and carboxybetaine methacrylamide. In addition, the light-triggered nature of the polymerization allows the creation of complex three-dimensional structures. The composition and topological structuring of the brushes are confirmed by X-ray photoelectron spectroscopy and atomic force microscopy. The kinetics of the polymerizations are followed by measuring the layer thickness with ellipsometry. The polymer brushes demonstrate excellent antifouling properties when exposed to single-protein solutions and complex biological matrices such as diluted bovine serum. This method thus presents a new simple approach for the manufacturing of antifouling coatings for biomedical and biotechnological applications.
