Surface coatings with so-called protein-repellent or nonfouling polymers have become indispensable for the development of modern therapeutic and diagnostic medical devices such as biosensors, drug-delivery capsules, and biomedical implants. Nowadays, poly(ethylene glycol) (PEG) is routinely used for these purposes. However, there is increasing evidence that PEG has limited long-term stability, particularly in vivo. Here we investigate poly(2-methyl-2-oxazoline) (PMOXA) as a potential alternative polymer. We designed comb copolymers consisting of a polycationic poly(l-lysine) backbone and PMOXA side chains by analogy to precisely studied and highly protein-repellent PEG-based systems. Using optical waveguide lightmode spectroscopy, we quantitatively compare the in situ self-assembly of the comb copolymers on negatively charged surfaces and the exposure of the formed monolayers to full human serum. We find that the PMOXA-based coatings with an optimal side-chain grafting density eliminate protein adsorption to a level of <2 ng/cm2; that is, they quantitatively equal the protein-repellent properties of the best PEG-based coatings.

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The prevention of surface fouling is becoming increasingly important for the development of anti-infective medical implants, biosensors with improved signal-to-noise ratios, and low-fouling membranes to name a few examples. We review a direct comparison of poly(ethylene glycol), the gold standard polymer to impart surfaces with nonfouling properties, to an alternative polymer, poly(2-methyl-2-oxazoline) (PMOXA), and show that both polymers are equally excellent in rendering surfaces nonfouling while PMOXA coatings are more stable in oxidative environments. We discuss prerequisites for the fabrication of nonfouling surface coatings and implications for the polymer choice according to application requirements.

Non-fouling surfaces that resist non-specific adsorption of proteins, bacteria, and higher organisms are of particular interest in diverse applications ranging from marine coatings to diagnostic devices and biomedical implants. Poly(ethylene glycol) (PEG) is the most frequently used polymer to impart surfaces with such non-fouling properties. Nevertheless, limitations in PEG stability have stimulated research on alternative polymers that are potentially more stable than PEG. Among them, we previously investigated poly(2-methyl-2-oxazoline) (PMOXA), a peptidomimetic polymer, and found that PMOXA shows excellent anti-fouling properties. Here, we compare the stability of films self-assembled from graft copolymers exposing a dense brush layer of PEG and PMOXA side chains, respectively, in physiological and oxidative media. Before media exposure both film types prevented the adsorption of full serum proteins to below the detection limit of optical waveguide in situ measurements. Before and after media exposure for up to 2 weeks, the total film thickness, chemical composition, and total adsorbed mass of the films were quantified using variable angle spectroscopic ellipsometry (VASE), X-ray photoelectron spectroscopy (XPS), and optical waveguide lightmode spectroscopy (OWLS), respectively. We found (i) that PMOXA graft copolymer films were significantly more stable than PEG graft copolymer films and kept their protein-repellent properties under all investigated conditions and (ii) that film degradation was due to side chain degradation rather than due to copolymer desorption.