Tunable Cell-Adhesive Surfaces by Surface-Initiated Photoinduced Electron-Transfer-Reversible Addition-Fragmentation Chain-Transfer Polymerization.

Cell adhesion involves many interactions between various molecules on the cell membrane (receptors, coreceptors, integrins, etc.) and surfaces or other cells. Cell adhesion plays a crucial role in the analysis of immune response, cancer treatment, tissue engineering, etc. Cell-cell adhesion can be quantified by measuring cell avidity, which defines the total interaction strength of the live cell binding. Typically, those investigations use tailor-made, reusable chips or surfaces onto which cells are cultured to form a monolayer to which other cells can bind. Cell avidity can then be measured by applying a force and quantifying cell-cell bond ruptures. The subsequent cleaning and reactivation of such biochip and biointeractive surfaces often require repeated etching, leading to device damage. Furthermore, it is often of great interest to harvest the cells that remain bound at the end of an avidity experiment for further analysis or use. It is, therefore, advantageous to pursue coating methods that allow tunable cell adhesion. This work presents temperature-switchable poly(di(ethylene glycol) methyl ether methacrylate) brush-based cell-interactive coatings produced by surface-initiated photoinduced electron-transfer reversible addition-fragmentation chain-transfer polymerization. The temperature switch of these brushes was explored by using a quartz crystal microbalance with dissipation monitoring, chemical composition, and physicochemical properties by atom force microscopy, X-ray photoelectron spectroscopy, single-molecule force spectroscopy, and ellipsometry.

SI-PET-RAFT in flow: improved control over polymer brush growth.

Surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) provides a light-dependent tool to synthesize polymer brushes on different surfaces that tolerates oxygen and water, and does not require a metal catalyst. Here we introduce improved control over SI-PET-RAFT polymerizations via continuous flow conditions. We confirm the composition and topological structure of the brushes by X-ray photoelectron spectroscopy, ellipsometry, and AFM. The improved control compared to no-flow conditions provides prolonged linear growth of the polymer brush (up to 250 nm, where no-flow polymerization maxed out <50 nm), and improved polymerization control of the polymer brush that allows the construction of diblock polymer brushes. We further show the linear correlation between the molecular weight of the polymer brush and its dry thickness by combining ellipsometry and single-molecule force spectroscopy.

Antiviral Polymer Brushes by Visible-Light-Induced, Oxygen-Tolerant Covalent Surface Coating.

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.

Alizarin Grafting onto Ultrasmall ZnO Nanoparticles: Mode of Binding, Stability, and Colorant Studies.

The demand is rising for colorants that are obtained from natural resources, tolerant to industrial processing methods, and meet color quality demands. Herein, we report how relevant properties such as thermal stability and photostability of the natural colorant alizarin can be improved by grafting it onto ZnO nanoparticles (NPs), allowing application in a warm extrusion process for the fabrication of polyamide fibers. For this study, ZnO NPs (diameter 2.0 ± 0.6 nm) were synthesized and subsequently functionalized with alizarin. The alizarin-coated ZnO NPs (i.e., dyed nanoparticles, DNPs) were characterized. Thermogravimetric analysis and ultraviolet-visible (UV-vis) studies revealed that alizarin coating accounts for ∼65% (w/w) of the total mass of the DNPs. A subsequent detailed characterization with Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), 13C cross-polarization magic angle spinning (CP-MAS) NMR, X-ray photoelectron spectroscopy (XPS), and quantum chemistry studies using various density functional theory (DFT) functionals and basis sets indicated that binding onto the ZnO NPs occurred predominantly via the catechol moiety of alizarin. Importantly, this grafting increased the thermal stability of alizarin with >100 °C, which allowed the processing of the DNPs into polyamide fibers by warm extrusion at 260 °C. Evaluation of the lightfastness of the DNP-dyed nylon fibers revealed that the changes in color quantified via the distance metric ΔE* of alizarin when embedded in a hybrid material were 2.6-fold better compared to nylon fibers that were directly dyed with alizarin. This reveals that the process of immobilization of a natural dye onto ZnO nanoparticles indeed improves the dye properties significantly and opens the way for a wide range of further studies into surface-immobilized dyes.

PLL-Poly(HPMA) Bottlebrush-Based Antifouling Coatings: Three Grafting Routes.

In this work, we compare three routes to prepare antifouling coatings that consist of poly(l-lysine)-poly(N-(2-hydroxypropyl)methacrylamide) bottlebrushes. The poly(l-lysine) (PLL) backbone is self-assembled onto the surface by charged-based interactions between the lysine groups and the negatively charged silicon oxide surface, whereas the poly(N-(2-hydroxypropyl)methacrylamide) [poly(HPMA)] side chains, grown by reversible addition-fragmentation chain-transfer (RAFT) polymerization, provide antifouling properties to the surface. First, the PLL-poly(HPMA) coatings are synthesized in a bottom-up fashion through a grafting-from approach. In this route, the PLL is self-assembled onto a surface, after which a polymerization agent is immobilized, and finally HPMA is polymerized from the surface. In the second explored route, the PLL is modified in solution by a RAFT agent to create a macroinitiator. After self-assembly of this macroinitiator onto the surface, poly(HPMA) is polymerized from the surface by RAFT. In the third and last route, the whole PLL-poly(HPMA) bottlebrush is initially synthesized in solution. To this end, HPMA is polymerized from the macroinitiator in solution and the PLL-poly(HPMA) bottlebrush is then self-assembled onto the surface in just one step (grafting-to approach). Additionally, in this third route, we also design and synthesize a bottlebrush polymer with a PLL backbone and poly(HPMA) side chains, with the latter containing 5% carboxybetaine (CB) monomers that eventually allow for additional (bio)functionalization in solution or after surface immobilization. These three routes are evaluated in terms of ease of synthesis, scalability, ease of characterization, and a preliminary investigation of their antifouling performance. All three coating procedures result in coatings that show antifouling properties in single-protein antifouling tests. This method thus presents a new, simple, versatile, and highly scalable approach for the manufacturing of PLL-based bottlebrush coatings that can be synthesized partly or completely on the surface or in solution, depending on the desired production process and/or application.

Antifouling Polymer Brushes via Oxygen-Tolerant Surface-Initiated PET-RAFT.

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.

Strain-Promoted Cycloaddition of Cyclopropenes with o-Quinones: A Rapid Click Reaction.

Novel click reactions are of continued interest in fields as diverse as bio-conjugation, polymer science and surface chemistry. Qualification as a proper "click" reaction requires stringent criteria, including fast kinetics and high conversion, to be met. Herein, we report a novel strain-promoted cycloaddition between cyclopropenes and o-quinones in solution and on a surface. We demonstrate the "click character" of the reaction in solution and on surfaces for both monolayer and polymer brush functionalization.