Christian Sarra-Bournet

A study of atmospheric pressure plasma discharges for surface functionalization of PTFE used in biomedical applications

Plasma polymer surface modification is widely used in the biomedical field to tailor the surface properties of materials to improve their biocompatibility. Most of these treatments are performed using low pressure plasma systems but recently, filamentary dielectric barrier discharge (FDBD) and atmospheric pressure glow discharge (APGD) have appeared as interesting alternatives. The aim of this paper is to evaluate the potential of surface modifications realized with FDBD and APGD in different atmospheres (N2+ H2 and N2+ NH3 mixtures) on poly(tetrafluoroethylene) to determine the relative influence of both the discharge regime and the gas nature on the surface transformations. From XPS analysis, it is shown that the discharge regime can have a significant effect on the surface transformation; FDBDs operating in H2/N2 lead to a high concentration of amino-groups with high specificity but also important damaging on the surface. Glow discharges in both H2/N2 and NH3/N2 lead to lower concentrations of amino-groups with lower specificity but lower surface damaging. Therefore, this simple surface treatment seems to be an effective, low cost method for the production of uniform surface modification with amino-groups that can subsequently be used to graft various chemical functionalities used for biomaterial compatibility.

Characterization of Multilayer Anti-Fog Coatings

Fog formation on transparent substrates constitutes a major challenge in several optical applications requiring excellent light transmission characteristics. Anti-fog coatings are hydrophilic, enabling water to spread uniformly on the surface rather than form dispersed droplets. Despite the development of several anti-fog coating strategies, the long-term stability, adherence to the underlying substrate, and resistance to cleaning procedures are not yet optimal. We report on a polymer-based anti-fog coating covalently grafted onto glass surfaces by means of a multistep process. Glass substrates were first activated by plasma functionalization to provide amino groups on the surface, resulting in the subsequent covalent bonding of the polymeric layers. The anti-fog coating was then created by the successive spin coating of (poly(ethylene-maleic anhydride) (PEMA) and poly(vinyl alcohol) (PVA) layers. PEMA acted as an interface by covalently reacting with both the glass surface amino functionalities and the PVA hydroxyl groups, while PVA added the necessary surface hydrophilicity to provide anti-fog properties. Each step of the procedure was monitored by XPS, which confirmed the successful grafting of the coating. Coating thickness was evaluated by profilometry, nanoindentation, and UV visible light transmission. The hydrophilic nature of the anti-fog coating was assessed by water contact angle (CA), and its anti-fog efficiency was determined visually and tested quantitatively for the first time using an ASTM standard protocol. Results show that the PEMA/PVA coating not only delayed the initial period required for fog formation but also decreased the rate of light transmission decay. Finally, following a 24 hour immersion in water, these PEMA/PVA coatings remained stable and preserved their anti-fog properties.

Effects of chemical composition and the addition of H2 in a N2 atmospheric pressure dielectric barrier discharge on polymer surface functionalization.

We examined the effect of hydrogen content in various polymers in a N2/H2 discharge for surface amine functionalization. Three polymers (polyethylene (PE), polyvinylidene fluoride (PVDF), and poly(tetrafluoroethylene) (PTFE)) containing various amounts of hydrogen and fluorine were treated with an atmospheric pressure dielectric barrier discharge (DBD). While surface modification was observed on the PE and the PVDF in a pure N2 discharge, adding H2 in a N2 discharge was necessary to observe the fluorine etching on the surface of the PVDF and PTFE polymers. The presence of a slight amount of hydrogen in the gas mixture was also a prerequisite to the formation of amino groups on the surface of all three polymers (max NH2/C approximately 5%). Aging revealed that the modified polymer surfaces treated in a N2-H2 discharge were less prone to hydrophobic recovery than were surfaces treated in pure N2, due primarily to the presence of a higher density of polar groups on the surfaces. We demonstrated that H atoms in the discharge are necessary for the surface amine functionalization of polymers in a N2 atmospheric pressure DBD, regardless of polymer chemical composition. It is therefore possible to control the plasma functionalization process and to optimize the concentration and specificity of NH2 grafted onto polymer surfaces by varying the H2 concentration in a N2 atmospheric pressure DBD.

Characterization of an air-spun poly(L-lactic acid) nanofiber mesh

It was previously showed that PLLA nanofiber mesh promoted good endothelial cell proliferation. A new technique was developed to produce nanofibers by air jet spinning inside the tubular shape of vascular prostheses and to characterize this nanofiber mesh. Polymer macromolecule stability was assessed by gel permeation chromatography. Thermal analyses were conducted with differential scanning calorimetry and dynamic mechanical analysis on PLLA nanofibers obtained with 4% and 7% solutions (w/v) in chloroform. Polyethylene terephthalate (PET) was also treated with atmospheric pressure dielectric barrier discharge under air or nitrogen atmosphere to optimize PLLA nanofiber adherence, assessed by peel tests. Air spinning induced a reduction of number-average molecular weight (M(n)) for the 7% PLLA solution but not for the 4% solution. The nanofibers were more crystalline and less sensible to viscoelastic relaxation as a function of aging in the 4% solution than in the 7% solution. Discharge treatment of the PET promoted identical surface modification on PET film and PET textile surfaces. Moreover, the best PLLA nanofibers adhesion results were obtained under nitrogen atmosphere. This study demonstrates that it is possible to coat the internal side of tubular vascular prostheses with PLLA nanofibers, and provides a better understanding of the air spinning process as well as optimizing nanofibers adhesion.

Rapid Nucleation of Iron Oxide Nanoclusters in Aqueous Solution by Plasma Electrochemistry

Progresses in cold atmospheric plasma technologies have made possible the synthesis of nanoparticles in aqueous solutions using plasma electrochemistry principles. In this contribution, a reactor based on microhollow cathodes and operating at atmospheric pressure was developed to synthesize iron-based nanoclusters (nanoparticles). Argon plasma discharges are generated at the tip of the microhollow cathodes, which are placed near the surface of an aqueous solution containing iron salts (FeCl2 and FeCl3) and surfactants (biocompatible dextran). Upon reaction at the plasma-liquid interface, reduction processes occur and lead to the nucleation of ultrasmall iron-based nanoclusters (IONCs). The purified IONCs were investigated by XPS and FTIR, which confirmed that the nucleated clusters contain a highly hydrated form of iron oxide, close to the stoichiometric constituents of α-FeOOH (goethite) or Fe5O3(OH)9 (ferrihydrite). Relaxivity values of r1 = 0.40 mM(-1) s(-1) and r2/r1 = 1.35 were measured (at 1.41 T); these are intermediate values between the relaxometric properties of superparamagnetic iron oxide nanoparticles used in medicine (USPIO) and those of ferritin, an endogenous contrast agent. Plasma-synthesized IONCs were injected into the mouse model and provided positive vascular signal enhancement in T1-w. MRI for a period of 10-20 min. Indications of rapid and strong elimination through the urinary and gastrointestinal tracts were also found. This study is the first to report on the development of a compact reactor suitable for the synthesis of MRI iron-based contrast media solutions, on site and upon demand.

Deposition of Functional Polymer Thin Films Using Atmospheric Pressure Plasma for Biomedical Applications – Endothelialization of Vascular Prostheses

Functionalized plasma polymer thin films were obtained in a dielectric barrier discharge at atmospheric pressure in an atmosphere of N2 and C2H4. The coatings were hydrophilic, adherent, chemically stable and presented a surface concentration of NH2 suitable for further biomolecule conjugation. Covalent grafting of a linking arm (glutaric anhydride) and subsequent conjugation of fibronectin, a protein of the extracellular matrix, were successful. Finally, endothelial cell adhesion experiments were performed directly on the functionalized thin films as well as on the conjugated coatings. Effects on cell adhesion were observed as a function of the plasma thin film deposition parameters.