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.
This Feature Article focuses on recent advances in the bioconjugation of surface-bound zwitterionic polymers for biospecific antifouling surfaces. Various approaches for the functionalization of antifouling zwitterionic polymers are systematically investigated, such as chain-end and side-chain functionalization. Side-chain functionalization methods can be further classified as those that are achieved through homopolymerization of custom-synthesized zwitterionic monomers equipped with reactive groups, or those that are achieved via synthesis of random or block copolymers combining different monomers with antifouling functionality and others with reactive groups. Several of the pros and cons of these approaches are outlined and discussed. Finally, some perspective and future directions of research are presented toward long-term stable, generically repelling surfaces that strongly and specifically adhere to a single component in a complex mixture.
The photoisomerization of the push-pull substituted azo dye Disperse Red 1 is studied using femtosecond time-resolved absorption spectroscopy and other spectroscopic and computational techniques. In comparison with azobenzene, the pipi* state is more stabilized by the effects of push-pull substitution than the npi* state, but the latter is probably still the lowest in energy. This conclusion is based on the kinetics, anisotropy of the excited state absorption spectrum, the spectra of the ground states, and quantum chemical calculations. The S(1)(npi*) state is formed from the initially excited pipi* state in <0.2 ps, and decays to the ground state with time constants of 0.9 ps in toluene, 0.5 ps in acetonitrile, and 1.4 ps in ethylene glycol. Thermal isomerization transforms the Z isomer produced to the more stable E isomer with time constants of 29 s (toluene), 28 ms (acetonitrile), and 2.7 ms (ethylene glycol). The pathway of photoisomerization is likely to be rotation about the N=N bond. Quantum chemical calculations indicate that along the inversion pathway ground and excited state energy surfaces remain well separated, whereas rotation leads to a region where conical intersections can occur. For the ground-state Z to E isomerization, conclusive evidence is lacking, but inversion is more probably the favored pathway in the push-pull substituted systems than in the parent azobenzene.
Zwitterionic poly(sulfobetaine acrylamide) (SBMAA) brushes were grafted from silicon-rich silicon nitride (SixN4, x > 3) surfaces by atom transfer radical polymerization (ATRP) and studied in protein adsorption experiments. To this aim ATRP initiators were immobilized onto SixN4 through stable Si-C linkages via three consecutive reactions. A UV-induced reaction of 1,2-epoxy-9-decene with hydrogen-terminated SixN4 surfaces was followed by conversion of the epoxide with 1,2-ethylenediamine resulting in primary and secondary amine-terminated surfaces. A reaction with 2-bromoisobutyryl bromide led to ATRP initiator-covered surfaces. Zwitterionic polymer brushes of SBMAA were grown from these initiator-coated surfaces (thickness ∼30 nm), and the polymer-coated surfaces were characterized in detail by static water contact angle measurements, X-ray photoelectron spectroscopy (XPS), and an atomic force microscope (AFM). The adsorption of proteins onto zwitterionic polymer coated surfaces was evaluated by in situ reflectometry, using a fibrinogen (FIB) solution of 0.1 g·L(-1), and compared to hexadecyl-coated SixN4 surfaces (C16-SixN4), uncoated air-based plasma oxidized SixN4 surfaces (SiOy-SixN4), and hexa(ethylene oxide)-coated SixN4 surfaces (EO6-SixN4). Excellent protein repellence (>99%) was observed for these zwitterionic polymer-coated SixN4 surfaces during exposure to FIB solution as compared to C16-SixN4 surfaces. Furthermore, the stability of these zwitterionic polymer-coated SixN4 surfaces was surveyed by exposing the surfaces for 1 week to phosphate buffered saline (PBS) solution at room temperature. The zwitterionic polymer-coated SixN4 surfaces before and after exposure to PBS solution were characterized by XPS, AFM, and water contact angle measurements, and their protein-repelling properties were evaluated by reflectometry. After exposure to PBS solution, the zwitterionic polymer coating remained intact, and its thickness was unchanged within experimental error. No hydrolysis was observed for the zwitterionic polymer after 1 week exposure to PBS solution, and the surfaces still repelled 98% FIB as compared to C16-SixN4 surfaces, demonstrating the long-term efficiency of these easily prepared surface coatings.
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