Plasma polymerization is gaining popularity as a technique for coating surfaces due to the low cost, ease of operation, and substrate-independent nature. Recently, the plasma polymerization (or deposition) of 2-oxazoline monomers was reported resulting in coatings that have potential applications in regenerative medicine. Despite the structural versatility of 2-oxazolines, only a few monomers have been subjected to plasma polymerization. Within this study, however, we explore the near atmospheric pressure plasma polymerization of a range of 2-oxazoline monomers, focusing on the influence of the aliphatic side-chain length (methyl to butyl) on the plasma polymerization process conditions as well as the properties of the obtained coatings. While side-chain length had only a minor influence on the chemical composition, clear effects on the plasma polymerization conditions were observed, thus gaining valuable insights in the plasma polymerization process as a function of monomer structure. Additionally, cytocompatibility and cell attachment on the coatings obtained by 2-oxazoline plasma polymerization was assessed. The coatings displayed strong cell interactive properties, whereby cytocompatibility increased with increasing aliphatic side-chain length of the monomer, reaching up to 93% cell viability after 1 day of cell culture compared to tissue culture plates. As this is in stark contrast to the antifouling behavior of the parent polymers, we compared the properties and composition of the plasma-polymerized coatings to the parent polymers revealing that a significantly different coating structure was obtained by plasma polymerization.

The plasma polymerization of amide-based precursors is a nearly unexplored research area, which is in contrast with the abundance of reports focusing on amidebased surface modification using wet chemistry. Therefore, this study aims to profoundly investigate the near-atmospheric pressure plasma polymerization of N,N-dimethylacrylamide (DMAM) to obtain stable coatings. In contrast to the unstable coatings obtained at lower discharge powers, the stable coatings that were obtained at higher powers showed a lower hydrophilicity as assessed by water contact angle (WCA). This decrease in hydrophilicity with increasing plasma power was found to be related to a reduced preservation of the monomer structure, as observed by Fourier transform infrared (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and XPS C 60 depth profiling, a rarely used but effective combination of techniques. Furthermore, the chemical composition of the coating was found to be in good agreement with the plasma active species observed by optical emission spectroscopy. Additionally, XPS C 60 depth profiling indicated a difference between the top layer and bulk of the plasma polymer due to spontaneous oxidation and/or postplasma coating deposition. Finally, the stable coatings were also found to have cell-interactive behavior toward MC3T3 as studied by in vitro live/dead fluorescence imaging and (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) (MTS) assays. With the latter technique, a cell viability of up to 89% as compared with tissue culture plates after 1 day of cell culture was observed, indicating the potential of these coatings for tissue engineering purposes.

Plasma polymerization has emerged as an appealing technique for surface modification because of its advantages over a variety of conventional techniques, including ease-of-use and the possibility to modify nearly any substrate. One of the main challenges of plasma polymer-based surface modification, however, is having control over the coating chemistry, as plasma deposition generates a diversity of chemical structures. Therefore, this study presents an alternative plasma-based method for the fabrication of coatings that contain selective functionalities. In a first step, hexamethyldisiloxane (HMDSO) plasma polymerization is performed in a medium-pressure dielectric barrier discharge (DBD) to deposit polydimethylsiloxane (PDMS)-like coatings. In a second step, this coating is exposed to an air plasma in a similar DBD setup to introduce silanol groups on the surface. These groups are used in a third and final step as anchoring points for grafting of (3aminopropyl)triethoxysilane (APTES) and (3-bromopropyl)trichlorosilane (BrPTCS) to selectively introduce amino or bromo groups, respectively. X-ray photoelectron spectroscopy (XPS) and water contact angle (WCA) measurements indicated that the first two steps were successful. Moreover, the coating could be synthesized on three different surfaces, namely, glass, ultrahigh-molecularweight polyethylene, and polytetrafluoroethylene, indicating the wide applicability of the developed procedure. Afterward, XPS also proved that the APTES and BrPTCS grafting resulted in the formation of a coating containing primary amines and alkyl bromides, respectively, in combination with an organosilicon matrix containing silanol groups as remaining reactive groups, proving the successful synthesis of selective functional plasma-based coatings. The intermediate air-plasma-activation step was demonstrated to be necessary for successful and stable grafting of the final layer. In conclusion, this study established a general procedure for the development of coatings with selective functionality that can be applied on a wide variety of substrates for, e.g., biosensor applications, biomolecule, or polymer immobilization or for the synthesis of antibacterial coatings.

No abstract

No abstract