Comparison of Plasma-Polymerized Thin Films Deposited from 2-Methyl-2-oxazoline and 2-Ethyl-2-oxazoline: I Film Properties.

Poly(2-oxazoline) is a promising new class of polymeric materials due to their antibiofouling properties and good biocompatibility. Poly(2-oxazoline) coatings can be deposited on different substrates via plasma polymerization, which can be more advantageous than other coating methods. The aim of this study is to deposit poly(2-oxazoline) coatings using a surface dielectric barrier discharge burning in nitrogen at atmospheric pressure using 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline vapours as monomers and compare the film properties. For the comparison, the antibacterial and cytocompatibility tests were peformed according to ISO norms. The antibacterial tests showed that all the deposited films were highly active against Staphylococcus aureus and Escherichia coli bacteria. The chemical composition of the films was studied using FTIR and XPS, and the film surface's properties were studied using AFM and surface energy measurement. The cytocompatibility tests showed good cytocompatibility of all the deposited films. However, the films deposited from 2-methyl-2-oxazoline exhibit better cytocompatibility. This difference can be explained by the different chemical compositions and surface morphologies of the films deposited from different monomers.

Antibacterial Thin Films Deposited from Propane-Butane Mixture in Atmospheric Pressure Discharge.

Antibacterial coatings on biomedical instruments are of great interest because they can suppress bacterial colonization on these instruments. In this study, antibacterial polymeric thin coatings were deposited on teflon substrates using atmospheric pressure plasma polymerization from a propane-butane mixture. The plasma polymerization was performed by means of surface dielectric barrier discharge burning in nitrogen at atmospheric pressure. The chemical composition of plasma polymerized propane-butane films was studied by energy-dispersive X-ray spectroscopy (EDX) and FTIR. The film surface properties were studied by SEM and by surface energy measurement. The EDX analysis showed that the films consisted of carbon, nitrogen and oxygen from ambient air. The FTIR analysis confirmed, in particular, the presence of alkyl, nitrile, acetylene, imide and amine groups. The deposited films were hydrophilic with a water contact angle in the range of 13-23°. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. On the other hand, the films were cytocompatible, reaching more than 80% of the cell viability threshold compared to reference polystyrene tissue.

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.

Restricted cell functions on micropillars are alleviated by surface-nanocoating with amino groups.

The topographical and chemical surface features of biomaterials are sensed by the cells, affecting their physiology at the interface. When placed on titanium, we recently discovered osteoblasts attempted caveolae-mediated phagocytosis of the sharp-edged microstructures. This active, energy-consuming process resulted in decreased osteoblastic cell functions (e.g. secretion of extracellular matrix proteins). However, chemical modification with plasma polymerized allylamine (PPAAm) was able to amplify osteoblast adhesion and spreading, resulting in better implant osseointegration in vivo In the present in vitro study, we analyzed whether this plasma polymer nanocoating is able to attenuate the microtopography-induced changes of osteoblast physiology. On PPAAm, we found cells showed a higher cell interaction with the geometrical micropillars by 30 min, and a less distinct reduction in the mRNA expression of collagen type I, osteocalcin and fibronectin after 24 h of cell growth. Interestingly, the cells were more active and sensitive on PPAAm-coated micropillars, and react with a substantial Ca2+ ion mobilization after stimulation with ATP. These results highlight that it is important for osteoblasts to establish cell surface contact for them to perform their functions.

Behaviour of Vascular Smooth Muscle Cells on Amine Plasma-Coated Materials with Various Chemical Structures and Morphologies.

Amine-coated biodegradable materials based on synthetic polymers have a great potential for tissue remodeling and regeneration because of their excellent processability and bioactivity. In the present study, we have investigated the influence of various chemical compositions of amine plasma polymer (PP) coatings and the influence of the substrate morphology, represented by polystyrene culture dishes and polycaprolactone nanofibers (PCL NFs), on the behavior of vascular smooth muscle cells (VSMCs). Although all amine-PP coatings improved the initial adhesion of VSMCs, 7-day long cultivation revealed a clear preference for the coating containing about 15 at.% of nitrogen (CPA-33). The CPA-33 coating demonstrated the ideal combination of good water stability, a sufficient amine group content, and favorable surface wettability and morphology. The nanostructured morphology of amine-PP-coated PCL NFs successfully slowed the proliferation rate of VSMCs, which is essential in preventing restenosis of vascular replacements in vivo. At the same time, CPA-33-coated PCL NFs supported the continuous proliferation of VSMCs during 7-day long cultivation, with no significant increase in cytokine secretion by RAW 264.7 macrophages. The CPA-33 coating deposited on biodegradable PCL NFs therefore seems to be a promising material for manufacturing small-diameter vascular grafts, which are still lacking on the current market.

Optical characterization of inhomogeneity of polymer-like thin films arising in the initial phase of plasma-enhanced chemical vapor deposition.

In this study, an optical investigation in a wide spectral range of polymer-like (SiOxCyHz) thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) is presented. The primary focus is on assessing the homogeneity of the grown films. Within the PECVD, it is possible to alter the properties of the deposited material by continually adjusting deposition process parameters and hence allow for the growth of inhomogeneous layers. However, as shown in this study, the growth of homogeneous layers could be similarly challenging. This challenge is especially pronounced at the beginning of the deposition process, where it is necessary to consider the influence of the substrate among other factors, as even slight variations in the deposition conditions can lead to the formation of inhomogeneous layers. Several series of polymer-like thin films were deposited onto silicon substrates with the goal of producing homogeneous layers, i.e. all deposition parameters were held constant. These samples were optically characterized with a special interest in homogeneity, especially at the beginning of the growth. It was found that initial inhomogeneous growth is always present. The thickness of the initial inhomogeneous part was found to be surprisingly large.

Human mesenchymal stromal cell adhesion and expansion on fluoropolymer surfaces modified with oxygen and nitrogen-rich plasma polymers.

Fluorinated ethylene propylene (FEP) vessels are of significant interest for therapeutic cell biomanufacturing applications due to their chemical inertness, hydrophobic surface, and high oxygen permeability. However, these properties also limit the adhesion and survival of anchorage-dependent cells. Here, we develop novel plasma polymer coatings to modify FEP surfaces, enhancing the adhesion and expansion of human mesenchymal stromal cells (hMSCs). Similar to commercially available tissue culture polystyrene vessels, oxygen-rich or nitrogen-rich surface chemistries can be achieved using this approach. While steam sterilization increased the roughness of the coatings and altered the surface chemistry, the overall wettability and oxygen or nitrogen-rich nature of the coatings were maintained. In the absence of proteins during initial cell attachment, cells adhered to surfaces even in the presence of chelators, whereas adhesion was abrogated with chelator in a protein-containing medium, suggesting that integrin-mediated adhesion predominates over physicochemical tethering in normal protein-containing cell seeding conditions. Albumin adsorption was more elevated on nitrogen-rich coatings compared to the oxygen-rich coatings, which was correlated with a higher extent of hMSC expansion after 3 days. Both the oxygen and nitrogen-rich coatings significantly improved hMSC adhesion and expansion compared to untreated FEP. FEP surfaces with nitrogen-rich coatings were practically equivalent to commercially available standard tissue culture-treated polystyrene surfaces in terms of hMSC yields. Plasma polymer coatings show significant promise in expanding the potential usage of FEP-based culture vessels for cell therapy applications.

From Basics to Frontiers: A Comprehensive Review of Plasma-Modified and Plasma-Synthesized Polymer Films.

This comprehensive review begins by tracing the historical development and progress of cold plasma technology as an innovative approach to polymer engineering. The study emphasizes the versatility of cold plasma derived from a variety of sources including low-pressure glow discharges (e.g., radiofrequency capacitively coupled plasmas) and atmospheric pressure plasmas (e.g., dielectric barrier devices, piezoelectric plasmas). It critically examines key operational parameters such as reduced electric field, pressure, discharge type, gas type and flow rate, substrate temperature, gap, and how these variables affect the properties of the synthesized or modified polymers. This review also discusses the application of cold plasma in polymer surface modification, underscoring how changes in surface properties (e.g., wettability, adhesion, biocompatibility) can be achieved by controlling various surface processes (etching, roughening, crosslinking, functionalization, crystallinity). A detailed examination of Plasma-Enhanced Chemical Vapor Deposition (PECVD) reveals its efficacy in producing thin polymeric films from an array of precursors. Yasuda's models, Rapid Step-Growth Polymerization (RSGP) and Competitive Ablation Polymerization (CAP), are explained as fundamental mechanisms underpinning plasma-assisted deposition and polymerization processes. Then, the wide array of applications of cold plasma technology is explored, from the biomedical field, where it is used in creating smart drug delivery systems and biodegradable polymer implants, to its role in enhancing the performance of membrane-based filtration systems crucial for water purification, gas separation, and energy production. It investigates the potential for improving the properties of bioplastics and the exciting prospects for developing self-healing materials using this technology.

Potential of plant secondary metabolite-based polymers to enhance wound healing.

There is a global epidemic of non-healing wounds. Chronic inflammation, overexpression of pro-inflammatory cytokines, oxidative stress and bacterial infection are implicated in delayed wound healing. Natural extracts are a rich source of bioactive molecules called plant secondary metabolites (PSMs) that include terpenes and phenols. These molecules may facilitate wound healing through their antioxidant, anti-inflammatory, and antibacterial activity. After briefly outlining the process of wound healing and how it is compromised in chronic wounds, this review focuses on investigating how PSMs-based polymers may improve wound healing. Best methods for incorporating PSMs into wound dressings are reviewed and critically compared. The exiting body of literature strongly suggests that PSMs-based polymers incorporated into wound dressings could have clinical value in aiding wound healing. STATEMENT OF SIGNIFICANCE: Chronic wounds develop by the persistence of inflammation, oxidative stress and infection. Chronic wounds affect the worldwide population, by reducing quality of life of patients with significant cost to healthcare systems. To help chronic wounds to heal and overcome this burden, materials with anti-inflammatory, antioxidant and antibacterial properties are required. Plant secondary metabolites (PSMs) are volatile materials that have all these properties. PSMs-based polymers can be fabricated by polymerization techniques. The present review provides an overview of the state-of-the-art of the wound healing mechanisms of PSMs. Current developments in the field of PSMs-based polymers are reviewed and their potential use as wound dressings is also covered.

Upcycle hazard against other hazard: Toxic fluorides from plasma fluoropolymer etching turn novel microbial disinfectants.

The release of toxic fluoride byproducts is a seemingly unavoidable artifact of surface engineering, causing severe environmental and human health problems. Here we propose and implement a new "upcycle hazard against other hazard" concept in the case study of cold atmospheric plasma surface modification of fluoropolymers such as polytetrafluorethylene (PTFE). Capitalizing on the excellent controllability, precision and energy efficiency of the plasma surface processing, complemented with the recently discovered ability of plasmas to activate water to produce a potent electrochemical disinfectant, referred to as the plasma-activated water (PAW), we demonstrate a radically new solution to capture the hazardous gaseous fluorides into the PAW and use the as-fluorinated PAW (F-PAW) as a very effective antimicrobial disinfectant. A customized surface discharge reactor is developed to evaluate the effects of fluorides released from the plasma etching of PTFE on the chemistries in gas-phase plasmas and F-PAW, as well as the antibacterial effect of F-PAW. The results show that gaseous fluorides, including COF2, CF3COF, and SiF4 are produced in gas-phase plasmas, and the dissolution of thus-generated fluorides into PAW has a strong effect on inactivating catalase and destroying the oxidation resistance of bacterial cells. As a result, the antibacterial effect of PAW-fluorides against the methicillin-resistant Staphylococcus aureus (MRSA) is enhanced by > 5 log reductions, suggesting that otherwise hazardous fluorides from the plasma processing of PTFE can be used to enhance the microbial disinfection efficiency of PAW. The demonstrated approach opens new avenues for sustainable hazard valorization exemplified by converting toxic fluoride-etching products into potent antimicrobial and potentially anti-viral disinfectants.

Candida albicans Can Survive Antifungal Surface Coatings on Surfaces with Microcone Topography.

This study demonstrates the ability of Candida albicans, a medically significant human fungal pathogen, to minimize contact with an antifungal surface coating that on a flat surface is lethal on contact by growing on and between micron-sized surface topographical features, thus minimizing the contact area. Scanning electron microscopy showed that cells contacting the "floor" between microcones were killed, whereas cells attached to microcones survived and formed hyphal filaments. These spanned space between cones and avoided contact with the flat surface in-between cones. Thus, fungal cells managed to attach and grow despite the antifungal coating. This ability of Candida albicans to exploit topography features to minimize surface contact yet utilize the solid surface for anchoring reduces the effectiveness of the grafted antifungal surface coating. This suggests that biomedical devices with rough surfaces might be more challenging to protect against fungal biofilm formation via application of an antifungal coating.

Plasma polymer surface modified expanded polytetrafluoroethylene promotes epithelial monolayer formation in vitro and can be transplanted into the dystrophic rat subretinal space.

The aim of this study was to evaluate whether the surface modification of expanded polytetrafluoroethylene (ePTFE) using an n-heptylamine (HA) plasma polymer would allow for functional epithelial monolayer formation suitable for subretinal transplant into a non-dystrophic rat model. Freshly isolated iris pigment epithelial (IPE) cells from two rat strains (Long Evans [LE] and Dark Agouti [DA]) were seeded onto HA, fibronectin-coated n-heptylamine modified (F-HA) and unmodified ePFTE and fibronectin-coated tissue culture (F-TCPS) substrates. Both F-HA ePTFE and F-TCPS substrates enabled functional monolayer formation with both strains of rat. Without fibronectin coating, only LE IPE formed a monolayer on HA-treated ePTFE. Functional assessment of both IPE strains on F-HA ePTFE demonstrated uptake of POS that increased significantly with time that was greater than control F-TCPS. Surgical optimization using Healon GV and mixtures of Healon GV: phosphate buffered saline (PBS) to induce retinal detachment demonstrated that only Healon GV:PBS allowed F-HA ePTFE substrates to be successfully transplanted into the subretinal space of Royal College of Surgeons rats, where they remained flat beneath the neural retina for up to 4 weeks. No apparent substrate-induced inflammatory response was observed by fundus microscopy or immunohistochemical analysis, indicating the potential of this substrate for future clinical applications.

Shelf-Life Optimisation of Plasma Polymerised (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPOpp) Coatings; A New Possible Approach to Tackle Infections in Chronic Wounds.

Chronic wounds fail to heal and are accompanied by an ongoing infection. They cause suffering, shorten lifespans, and their prevalence is increasing. Unfortunately, the medical treatment of chronic wounds has remained unchanged for decades. A novel approach to break the biological vicious cycle is the long-lived radical (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO). TEMPO can be plasma polymerised (TEMPOpp) into thin coatings that have antimicrobial properties. However, due to its radical nature, quenching causes it to lose effectiveness over time. Our aim in this study was to extend the shelf-life of TEMPOpp coatings using various storage conditions: Namely, room temperature (RT), room temperature & vacuum sealed (RTV), freezer temperature & vacuum sealed (FTV). We have analysed the coatings' quality via the surface analytical methods of X-Ray Photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR); finding marked differences among the three storage conditions. Furthermore, we have compared the antimicrobial efficacy of the stored coatings against two major bacterial pathogens, Staphylococcus aureus and Staphylococcus epidermidis, commonly found in chronic wounds. We did so both qualitatively via live/dead staining, as well as quantitatively via (2-methoxy-4-nitro-5-sulfophenyl)-5-[(phenylamino) carbonyl]-2H-tetrazolium (XTT) viability assay for up to 15 weeks in 5 weeks increments. Taken all together, we demonstrate that samples stored under FTV conditions retain the highest antimicrobial activity after 15 weeks and that this finding correlates with the retained concentration of nitroxides.

Atmospheric Pressure Plasma Polymerized 2-Ethyl-2-oxazoline Based Thin Films for Biomedical Purposes.

Polyoxazoline thin coatings were deposited on glass substrates using atmospheric pressure plasma polymerization from 2-ethyl-2-oxazoline vapours. The plasma polymerization was performed in dielectric barrier discharge burning in nitrogen at atmospheric pressure. The thin films stable in aqueous environments were obtained at the deposition with increased substrate temperature, which was changed from 20 ∘C to 150 ∘C. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. The chemical composition of polyoxazoline films was studied by FTIR and XPS, the mechanical properties of films were studied by depth sensing indentation technique and by scratch tests. The film surface properties were studied by AFM and by surface energy measurement. After tuning the deposition parameters (i.e., monomer flow rate and substrate temperature), stable films, which resist bacterial biofilm formation and have cell-repellent properties, were achieved. Such antibiofouling polyoxazoline thin films can have many potential biomedical applications.

Plasma-Polymer-Fluorocarbon Thin Film Coated Nanostructured-Polyethylene Terephthalate Surface with Highly Durable Superhydrophobic and Antireflective Properties.

Herein, an antireflection and superhydrophobic film was obtained by uniformly forming nanostructures on the surface of polyethylene terephthalate (PET) substrate using oxygen plasma without a pattern mask and coating plasma-polymer-fluorocarbon (PPFC) on the nanostructured surface by mid-range frequency sputtering. PPFC/nanostructured-PET showed a reflectance of 4.2%, which is 56% lower than that of the PET film. Haze was also improved. Nanostructured-PET exhibited a superhydrophilic surface due to plasma deformation and a superhydrophobic surface could be realized by coating PPFC on the nanostructured surface. The PPFC coating prevented the aging of polymer film nanostructures and showed excellent durability in a high-temperature and high-humidity environment. It exhibited excellent flexibility to maintain the superhydrophobic surface, even at a mechanical bending radius of 1 mm, and could retain its properties even after repeated bending for 10,000 times.

A multifaceted biomimetic interface to improve the longevity of orthopedic implants.

The rise of additive manufacturing has provided a paradigm shift in the fabrication of precise, patient-specific implants that replicate the physical properties of native bone. However, eliciting an optimal biological response from such materials for rapid bone integration remains a challenge. Here we propose for the first time a one-step ion-assisted plasma polymerization process to create bio-functional 3D printed titanium (Ti) implants that offer rapid bone integration. Using selective laser melting, porous Ti implants with enhanced bone-mimicking mechanical properties were fabricated. The implants were functionalized uniformly with a highly reactive, radical-rich polymeric coating generated using a unique combination of plasma polymerization and plasma immersion ion implantation. We demonstrated the performance of such activated Ti implants with a focus on the coating's homogeneity, stability, and biological functionality. It was shown that the optimized coating was highly robust and possessed superb physico-chemical stability in a corrosive physiological solution. The plasma activated coating was cytocompatible and non-immunogenic; and through its high reactivity, it allowed for easy, one-step covalent immobilization of functional biomolecules in the absence of solvents or chemicals. The activated Ti implants bio-functionalized with bone morphogenetic protein 2 (BMP-2) showed a reduced protein desorption and a more sustained osteoblast response both in vitro and in vivo compared to implants modified through conventional physisorption of BMP-2. The versatile new approach presented here will enable the development of bio-functionalized additively manufactured implants that are patient-specific and offer improved integration with host tissue. STATEMENT OF SIGNIFICANCE: Additive manufacturing has revolutionized the fabrication of patient-specific orthopedic implants. Although such 3D printed implants can show desirable mechanical and mass transport properties, they often require surface bio-functionalities to enable control over the biological response. Surface covalent immobilization of bioactive molecules is a viable approach to achieve this. Here we report the development of additively manufactured titanium implants that precisely replicate the physical properties of native bone and are bio-functionalized in a simple, reagent-free step. Our results show that covalent attachment of bone-related growth factors through ion-assisted plasma polymerized interlayers circumvents their desorption in physiological solution and significantly improves the bone induction by the implants both in vitro and in vivo.

Modulation of substrate van der Waals forces using varying thicknesses of polymer overlayers.

Thin polymeric coatings are commonly used for altering surface properties and modulating the interfacial performance of materials. Possible contributions from the substrate to the interfacial forces and effects are, however, usually ignored and are not well understood, nor is it established how the coating thickness modulates and eventually eliminates contributions from substrates to the van der Waals (vdW) interfacial force. In this study we quantified, by colloid-probe atomic force microscope (AFM) and by theoretical calculations, the interfacial vdW contributions from substrates acting through ethanol plasma polymer (EtOHpp) coatings of a range of thicknesses on Au and Si bulk materials. In approach force curves against EtOHpp-coated Au substrates the magnitude of the vdW force decreased as the EtOHpp coating thickness increased to 18 nm and then plateaued with further increases in coating thickness, providing direct evidence for a contribution to the total interfacial vdW force from the Au substrate acting through thin coatings. The experimental observations accord with theoretical calculations of the thickness dependence of Hamaker coefficients derived from rigorous simulation using the Lifshitz theory. In addition, the measured forces agree well with theoretical predictions including correction for finite roughness. Thus, our experimental and theoretical results establish how the thickness of polymer thin film coatings modulates the total interfacial vdW force and how this can be used to tune the net vdW force so as to either contain a large substrate contribution or arise predominantly from the polymeric overlayer. Our findings enable rational design of coating thickness to tailor interfacial interactions and material performance.

Atmospheric Pressure Plasma Polymerized Oxazoline-Based Thin Films-Antibacterial Properties and Cytocompatibility Performance.

Polyoxazolines are a new promising class of polymers for biomedical applications. Antibiofouling polyoxazoline coatings can suppress bacterial colonization of medical devices, which can cause infections to patients. However, the creation of oxazoline-based films using conventional methods is difficult. This study presents a new way to produce plasma polymerized oxazoline-based films with antibiofouling properties and good biocompatibility. The films were created via plasma deposition from 2-methyl-2-oxazoline vapors in nitrogen atmospheric pressure dielectric barrier discharge. Diverse film properties were achieved by increasing the substrate temperature at the deposition. The physical and chemical properties of plasma polymerized polyoxazoline films were studied by SEM, EDX, FTIR, AFM, depth-sensing indentation technique, and surface energy measurement. After tuning of the deposition parameters, films with a capacity to resist bacterial biofilm formation were achieved. Deposited films also promote cell viability.

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.

Fast Surface Hydrophilization via Atmospheric Pressure Plasma Polymerization for Biological and Technical Applications.

Polymeric surfaces can benefit from functional modifications prior to using them for biological and/or technical applications. Surfaces considered for biocompatibility studies can be modified to gain beneficiary hydrophilic properties. For such modifications, the preparation of highly hydrophilic surfaces by means of plasma polymerization can be a good alternative to classical wet chemistry or plasma activation in simple atomic or molecular gasses. Atmospheric pressure plasma polymerization makes possible rapid, simple, and time-stable hydrophilic surface preparation, regardless of the type and properties of the material whose surface is to be modified. In this work, the surface of polypropylene was coated with a thin nanolayer of plasma-polymer which was prepared from a low-concentration mixture of propane-butane in nitrogen using atmospheric pressure plasma. A deposition time of only 1 second was necessary to achieve satisfactory hydrophilic properties. Highly hydrophilic, stable surfaces were obtained when the deposition time was 10 seconds. The thin layers of the prepared plasma-polymer exhibit highly stable wetting properties, they are smooth, homogeneous, flexible, and have good adhesion to the surface of polypropylene substrates. Moreover, they are constituted from essential elements only (C, H, N, O). This makes the presented modified plasma-polymer surfaces interesting for further studies in biological and/or technical applications.