Atmospheric pressure plasma liquid assisted deposition of polydopamine/acrylate copolymer on zirconia (Y-TZP) ceramics: a biocompatible and adherent nanofilm.

Polydopamine-ethylene glycol dimethacrylate copolymer is a biocompatible coating with cell adhesion promotion and antibiofilm properties. This copolymer has been successfully applied on metallic implants, such as stainless steel and titanium implants, using several deposition techniques (e.g. layer-by-layer, silane activation, chemical vapor deposition, or liquid-assisted plasma polymerization). However, its application in zirconia ceramic materials, which are widely used in dentistry and medicine, has never been described. In this work, polydopamine-ethylene glycol dimethacrylate copolymer has been deposited on ultra-smooth surfaces of yttria-stabilized zirconia discs (average roughness = 2.08 ± 0.08 nm) by using liquid-assisted atmospheric-pressure plasma-induced polymerization (LA-APPiP). After the polymerization, the nanometric coating (250 nm, measured by ellipsometry) had an average roughness of 79.85 ± 13.71 nm and water contact angle of 57.8 ± 2.2 degrees, consistent with the highly hydrophilic nature of the biocompatible copolymer, if compared to the pristine zirconia (72.7 ± 2.0 degrees). The successful covalent bonding of the copolymer with the zirconia surface, thanks to the previous activation of the substrate with oxygen plasma, was proved by X-ray photoelectron spectroscopy (XPS). The polymer composition has been investigated by XPS and Raman spectroscopies. The LA-APPiP technique has been proved to be an excellent method to produce homogenous films without the need to employ solvents and further purification steps. The new copolymer film allows the uniform growth of human osteoblast-like MG-63 cells, after 7 days of cell culture, as observed by fluorescence microscopy.

Anti-biofouling activity of Ranaspumin-2 bio-surfactant immobilized on catechol-functional PMMA thin layers prepared by atmospheric plasma deposition.

The deposition of polymeric thin layers bearing reactive functional groups is a promising solution to provide functionality on otherwise inert surfaces, for instance, for bioconjugation purposes. Atmospheric pressure plasma (AP plasma) deposition technology offers many advantages, such as fast deposition rates, low costs, low waste generation and suitability for coating various kind of material surfaces. In this work, the AP plasma-assisted copolymerization of methyl methacrylate (MMA) with a vinyl derivative of L-DOPA was studied in order to deposit coatings with reactive catechol/quinone groups suitable for protein covalent immobilization. The effect of adding a chemical cross-linker, between 0 and 2 mol%, to the monomer mixture is also studied in order to prepare robust plasma PMMA-based layers in liquid physiological media. The layer prepared with 0.2 mol% of cross-linker shows the best balance between stability in saline-buffered media and surface functionalization. Bioconjugation via the grafting of Ranaspumin-2 recombinant, a naturally occurring surfactant protein, is carried out in a single step after plasma deposition. Protein immobilization is corroborated by Quartz Crystal Microbalance with Dissipation (QCM-D) and Surface Plasmon Resonance (SPR) analyses and confirmed via Epicocconone staining, X-Ray Photoemission Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) measurements and surface wettability characterizations. The bio-functionalized layers presented an enhanced activity against the adhesion of Human Serum Albumin (HSA), indicating the grafting potential of the Ranaspumin-2 bio-surfactant to produce anti-biofouling functional coatings.

Atmospheric Plasma Deposition of Methacrylate Layers Containing Catechol/Quinone Groups: An Alternative to Polydopamine Bioconjugation for Biomedical Applications.

Bioconjugation of enzymes on coatings based on polydopamine (PDA) layers is an appealing approach to control biological responses on biomedical implant surfaces. As alternative to PDA wet deposition, a fast, solvent-free, and dynamic deposition approach based on atmospheric-pressure plasma dielectric barrier discharge process is considered to deposit on metallic surfaces acrylic-based interlayers containing highly chemically reactive catechol/quinone groups. A biomimetic approach based on covalent immobilization of Dispersin B, an enzyme with antibiofilm properties, shows the bioconjugation potential of the novel plasma polymer layers. The excellent antibiofilm activity against Staphylococcus epidermidis is comparable to the PDA-based layers prepared by wet chemical methods with slow deposition rates. A study of preosteoblastic MG-63 human cell line viability and adhesion properties on plasma polymer layers demonstrates early interaction required for biomedical applications.