Decontamination-Induced Modification of Bioactivity in Essential Oil-Based Plasma Polymer Coatings

Plasma polymer coatings fabricated from Melaleuca alternifolia essential oil and its derivatives have been previously shown to reduce the extent of microbial adhesion on titanium, polymers, and other implantable materials used in dentistry. Previous studies have shown these coatings to maintain their performance under standard operating conditions; however, when used in e.g., a dental implant, these coatings may inadvertently become subject to in situ cleaning treatments, such as those using an atmospheric pressure plasma jet, a promising tool for the effective in situ removal of biofilms from tissues and implant surfaces. Here, we investigated the effect of such an exposure on the antimicrobial performance of the Melaleuca alternifolia polymer coating. It was found that direct exposure of the polymer coating surface to the jet for periods less than 60 s was sufficient to induce changes in its surface chemistry and topography, affecting its ability to retard subsequent microbial attachment. The exact effect of the jet exposure depended on the chemistry of the polymer coating, the length of plasma treatment, cell type, and incubation conditions. The change in the antimicrobial activity for polymer coatings fabricated at powers of 20–30 W was not statistically significant due to their limited baseline bioactivity. Interestingly, the bioactivity of polymer coatings fabricated at 10 and 15 W against Staphylococcus aureus cells was temporarily improved after the treatment, which could be attributed to the generation of loosely attached bioactive fragments on the treated surface, resulting in an increase in the dose of the bioactive agents being eluted by the surface. Attachment and proliferation of Pseudomonas aeruginosa cells and mixed cultures were less affected by changes in the bioactivity profile of the surface. The sensitivity of the cells to the change imparted by the jet treatment was also found to be dependent on their origin culture, with mature biofilm-derived P. aeruginosa bacterial cells showing a greater ability to colonize the surface when compared to its planktonic broth-grown counterpart. The presence of plasma-generated reactive oxygen and nitrogen species in the culture media was also found to enhance the bioactivity of polymer coatings fabricated at power levels of 10 and 15 W, due to a synergistic effect arising from simultaneous exposure of cells to reactive oxygen and nitrogen species (RONS) and eluted bioactive fragments. These results suggest that it is important to consider the possible implications of inadvertent changes in the properties and performance of plasma polymer coatings as a result of exposure to in situ decontamination, to both prevent suboptimal performance and to exploit possible synergies that may arise for some polymer coating-surface treatment combinations.

Pyrrole Plasma Polymer-Coated Electrospun Scaffolds for Neural Tissue Engineering

Promising strategies for neural tissue engineering are based on the use of three-dimensional substrates for cell anchorage and tissue development. In this work, fibrillar scaffolds composed of electrospun randomly- and aligned-oriented fibers coated with plasma synthesized pyrrole polymer, doped and undoped with iodine, were fabricated and characterized. Infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction analysis revealed the functional groups and molecular integration of each scaffold, as well as the effect of plasma polymer synthesis on crystallinity. Scanning microscopy imaging demonstrated the porous fibrillar micrometric structure of the scaffolds, which afforded adhesion, infiltration, and survival for the neural cells. Orientation analysis of electron microscope images confirmed the elongation of neurite-like cell structures elicited by undoped plasma pyrrole polymer-coated aligned scaffolds, without any biochemical stimuli. The MTT colorimetric assay validated the biocompatibility of the fabricated composite materials, and further evidenced plasma pyrrole polymer-coated aligned scaffolds as permissive substrates for the support of neural cells. These results suggest plasma synthesized pyrrole polymer-coated aligned scaffolds are promising materials for tissue engineering applications.

Sensitivity Enhancement in Plasma Polymer Films for Surface Acoustic Wave Based Sensor Applications

Plasma polymer films (PPF), widely used as sensing layers in surface acoustic wave (SAW) based gas and liquid phase sensors, have a major drawback: high concentrations of the sensed analytes easily drive these films into saturation, where accurate measurements are no longer possible. This work suggests a solution to this problem by modifying the PPF with the sensed chemical compound to improve the overall sorption properties and sensor dynamic range. Thin polymer films were synthesized from hexamethyldisiloxane (HMDSO) and triethylsilane (TES) monomers in a plasma-enhanced chemical vapor deposition (PECVD) process using a RF plasma reactor. We used these Si-containing compounds because they are known for their excellent sensing properties. In this work, the layers were deposited onto the active surface of high-Q 438 MHz Rayleigh SAW two-port resonators, used as mass sensitive sensor elements. We call these devices quartz surface microbalances (QSM). In a second step, ammonia plasma modification was applied to the HMDSO and TES films, in order to achieve a higher sensitivity to NH3. The sensors were probed at different NH3 gas concentrations in a computer controlled gas probing setup. A comparison with unmodified films revealed a 74% to 85% improvement in both the sensitivity and sorption ability of the HMDSO sensing layers, and of about 8% for the TES films.

Comparative Study of Natural Terpenoid Precursors in Reactive Plasmas for Thin Film Deposition

If plasma polymer thin films are to be synthesised from sustainable and natural precursors of chemically heterogeneous composition, it is important to understand the extent to which this composition influences the mechanism of polymerisation. To this end, a well-studied monoterpene alcohol, terpinen-4-ol, has been targeted for a comparative study with the naturally occurring mix of terpenes (viz. Melaleuca alternifolia oil) from which it is commonly distilled. Positive ion mode mass spectra of both terpinen-4-ol and M. alternifolia oil showed a decrease in disparities between the type and abundance of cationic species formed in their respective plasma environments as applied plasma power was increased. Supplementary biological assay revealed the antibacterial action of both terpinen-4-ol and M. alternifolia derived coatings with respect to S. aureus bacteria, whilst cytocompatibility was demonstrated by comparable eukaryotic cell adhesion to both coatings. Elucidating the processes occurring within the reactive plasmas can enhance the economics of plasma polymer deposition by permitting use of the minimum power, time and precursor pre-processing required to control the extent of monomer fragmentation and fabricate a film of the desired thickness and functionality.

Bioactive Plasma Coatings on Orthodontic Brackets: In Vitro Metal Ion Release and Cytotoxicity

The metal ion release characteristics and biocompatibility of meta-based materials are key factors that influence their use in orthodontics. Although stainless steel-based alloys have gained much interest and use due to their mechanical properties and cost, they are prone to localised attack after prolonged exposure to the hostile oral environment. Metal ions may induce cellular toxicity at high dosages. To circumvent these issues, orthodontic brackets were coated with a functional nano-thin layer of plasma polymer and further immobilised with enantiomers of tryptophan. Analysis of the physicochemical properties confirmed the presence of functional coatings on the surface of the brackets. The quantification of metal ion release using mass spectrometry proved that plasma functionalisation could minimise metal ion release from orthodontic brackets. Furthermore, the biocompatibility of the brackets has been improved after functionalisation. These findings demonstrate that plasma polymer facilitated surface functionalisation of orthodontic brackets is a promising approach to reducing metal toxicity without impacting their bulk properties.

Mechanical properties of plasma polymer films: a review

Plasma polymers are micro-, or more commonly, nano-sized coatings that can be deposited on a variety of substrates through different approaches. The versatility of these polymers is incremented by the possibility to use other precursors than conventional polymerization reactions and by potential changes in the polymerization mechanisms according to the intrinsic physical and chemical properties of the plasma. That flexibility offers a fruitful ground to a great range of scientific and engineering fields, but it also brings many challenges for universalization of empirical observations. In this review, the use of different precursors, substrates and changes in plasma external parameters were evaluated as common, but not necessarily ideal nor exhaustive, variables for the analysis of mechanical properties of plasma polymer films. The commonly reported trends are complemented with the exceptions, and a variety of hypothesis drawn by the empirical observations are shown. The techniques and methods used for determining the mechanical properties of plasma polymers, the effect of post-treatments on them and some applications are evaluated. Finally, a general conclusion highlighting the challenges of the field is provided. Article highlights The mechanical properties of plasma polymers are evaluated as a function of selected parameters. The techniques of characterization of mechanical properties of plasma polymers are summarized. A discussion of future and current demands for the analysis of mechanical properties of plasma polymers is done.