Robust CA-GO-TiO2/PTFE Photocatalytic Membranes for the Degradation of the Azithromycin Formulation from Wastewaters.

We have developed an innovative thin-film nanocomposite membrane that contains cellulose acetate (CA) with small amounts of TiO2-decorated graphene oxide (GO) (ranging from 0.5 wt.% to 2 wt.%) sandwiched between two polytetrafluoroethylene (PTFE)-like thin films. The PTFE-like films succeeded in maintaining the bulk porosity of the support while increasing the thermal and chemical robustness of the membrane and boosting the catalytic activity of TiO2 nanoparticles. The membranes exhibited a specific chemical composition and bonding, with predominant carbon-oxygen bonds from CA and GO in the bulk, and carbon-fluorine bonds on their PTFE-like coated sides. We have also tested the membranes' photocatalytic activities on azithromycin-containing wastewaters, demonstrating excellent efficiency with more than 80% degradation for 2 wt.% TiO2-decorated GO in the CA-GO-TiO2/PTFE-like membranes. The degradation of the azithromycin formulation occurs in two steps, with reaction rates being correlated to the amount of GO-TiO2 in the membranes.

Mass Spectra Fitting as Diagnostic Tool for Magnetron Plasmas Generated in Ar and Ar/H2 Gases with Tungsten Targets.

In this work, we describe an ion mass spectra processing method from plasmas generated in Ar and Ar/H2 gases in contact with tungsten surfaces. For this purpose, advanced model functions, i.e., those suitable for fitting the experimental mass peak profiles, are used. In addition, the peak positions, peak shapes, abundances, and ion ratios are the parameters considered for building these functions. In the case of a multielement magnetron target, the calibration of the mass spectra with respect to the peak shape and position on the m/z scale is helpful in reducing the number of free variables during fitting. The mass spectra fitting procedure is validated by the obtained isotopic abundances of W ions in W/Ar magnetron plasmas, which, in turn, are comparable with their natural abundance. Moreover, its usefulness is exemplified by calculating the ratio of WH+/W+ ions in W/Ar/H2 plasma. This work paves the way for obtaining relevant results regarding ion species in plasma even in the case of using general-purpose mass spectrometers with limited resolution and accuracy. Although this method is illustrated for the W/Ar/H2 plasma system, it can be easily extendable to any plasma type.

Chemistry-Induced Effects on Cell Behavior upon Plasma Treatment of pNIPAAM.

In the field of bioengineering, depending on the required application, the attachment of various biological entities to the biomaterial is either favored or needs to be prevented. Therefore, different surfaces modification strategies were developed in combination with the characteristics of the materials. The present contribution reports on the use of the specific surface property of a thermoresponsive polymer poly(N-isopropylacrylamide) pNIPAAM obtained by spin coating in combination with plasma treatment for tuning cell behavior on treated polymeric surfaces. Topographical information for the plasma-treated pNIPAAM coatings obtained by Atomic Force Microscopy (AFM) measurements evidenced a more compact surface for Ar treatment due to combined etching and redeposition, while for oxygen, a clear increase of pores diameter is noticed. The chemical surface composition as determined by X-ray Photoelectron Spectroscopy showed the specific modifications induced by plasma treatment, namely strong oxidation for oxygen plasma treatment illustrated by eight times increase of O-C=O contribution and respectively an increase of C-N/O=C-N bonds in the case of ammonia plasma treatment. Structural information provided by FTIR spectroscopy reveals a significant increase of the carboxylic group upon argon and mostly oxygen plasma treatment and the increase in width and intensity of the amide-related groups for the ammonia plasma treatment. The biological investigations evidenced that L929 fibroblast cells viability is increased by 25% upon plasma treatment, while the cell attachment is up to 2.8 times higher for the oxygen plasma-treated surface compared to the initial spin-coated pNIPAAM. Moreover, the cell detachment process proved to be up to 2-3 times faster for the oxygen and argon plasma-treated surfaces and up to 1.5 times faster for the ammonia-treated surface. These results show the versatility of plasma treatment for inducing beneficial chemical modifications of pNIPAAM surfaces that allows the tuning of cellular response for improving the attachment-detachment process in view of tissue engineering.

Towards Understanding the Chemical Structure Modification of EVA Copolymer upon MAPLE Processing of Thin Films.

A series of coatings from poly(ethylene-co-vinyl acetate) (EVA) were obtained using the matrix-assisted pulsed laser evaporation (MAPLE) technique. By changing the process parameters, i.e., laser fluence and EVA co-polymer concentration in the target, coatings with various morphologies and topographies were produced. The evaluation of the film structure was based on an analysis of optical and atomic force microscopy and profilometry measurements. A detailed chemical structure investigation, conducted based on Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra, revealed that although the general structure was preserved, some alterations of ethylene (Et) and vinyl acetate (VAc) blocks took place. The most noticeable change was in the ester group that was transformed into ketone and carboxyl groups; nevertheless, some changes in the aliphatic main chain were also present. The chemical structure changes in EVA coatings took place regardless of the process parameters used. The use of chloroform as a solvent to dissolve the EVA copolymer was indicated as a possible reason of the changes as well as the tendency of EVA macromolecules to form clusters. Nevertheless, due to low level of structure alteration, it has been shown that the MAPLE technique can be successfully used to obtain coatings from polymers with more complex structures, which are soluble in a limited number of solvents.

One Step e-Beam Radiation Cross-Linking of Quaternary Hydrogels Dressings Based on Chitosan-Poly(Vinyl-Pyrrolidone)-Poly(Ethylene Glycol)-Poly(Acrylic Acid).

We report on the successful preparation of wet dressings hydrogels based on Chitosan-Poly(N-Vinyl-Pyrrolidone)-Poly(ethylene glycol)-Poly(acrylic acid) and Poly(ethylene oxide) by e-beam cross-linking in weakly acidic media, to be used for rapid healing and pain release of infected skin wounds. The structure and compositions of hydrogels investigated according to sol-gel and swelling studies, network parameters, as well as FTIR and XPS analyses showed the efficient interaction of the hydrogel components upon irradiation, maintaining the bonding environment while the cross-linking degree increasing with the irradiation dose and the formation of a structure with the mesh size in the range 11-67 nm. Hydrogels with gel fraction above 85% and the best swelling properties in different pH solutions were obtained for hydrogels produced with 15 kGy. The hydrogels are stable in the simulated physiological condition of an infected wound and show appropriate moisture retention capability and the water vapor transmission rate up to 272.67 g m-2 day-1, to ensure fast healing. The hydrogels proved to have a significant loading capacity of ibuprofen (IBU), being able to incorporate a therapeutic dose for the treatment of severe pains. Simultaneously, IBU was released up to 25% in the first 2h, having a release maximum after 8 h.

Combining Fluorinated Polymers with Ag Nanoparticles as a Route to Enhance Optical Properties of Composite Materials.

Polymer-based nanocomposites have recently received considerable attention due to their unique properties, which makes them feasible for applications in optics, sensors, energy, life sciences, etc. The present work focuses on the synthesis of nanocomposites consisting of a polytetrafluorethylene-like matrix in which metallic nano-silver are embedded, by using multiple magnetron plasmas. By successively exposing the substrate to separate RF magnetrons using as combination of target materials polytetrafluorethylene (PTFE) and silver, individual control of each deposition process is insured, allowing obtaining of structures in which silver nanoparticles are entrapped in-between two PTFE layers with given thicknesses. The topographical and morphological characteristics investigated by means of Scanning Electron Microscopy and Atomic Force Microscopy techniques evidenced the very presence of Ag nanoparticles with typical dimension 7 nm. The chemical composition at various depositing steps was evaluated through X-ray Photoelectron Spectroscopy. We show that the presence of the top PTFE layer prevents silver oxidation, while its thickness allows the tailoring of optical properties, as evidenced by spectroellipsometry. The appearance of chemical bonds between silver atoms and PTFE atoms at interfaces is observed, pointing out that despite of pure physical deposition processes, a chemical interaction between the polymeric matrix and metal is promoted by plasma.

Effect of Dispersion Solvent on the Deposition of PVP-Silver Nanoparticles onto DBD PlasmaTreated Polyamide 6,6 Fabric and Its Antimicrobial Efficiency.

Polyvinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs) dispersed in ethanol, water and water/alginate were used to functionalize untreated and dielectric barrier discharge (DBD) plasma-treated polyamide 6,6 fabric (PA66). The PVP-AgNPs dispersions were deposited onto PA66 by spray and exhaustion methods. The exhaustion method showed a higher amount of deposited AgNPs. Water and water-alginate dispersions presented similar results. Ethanol amphiphilic character showed more affinity to AgNPs and PA66 fabric, allowing better uniform surface distribution of nanoparticles. Antimicrobial effect in E. coli showed good results in all the samples obtained by exhaustion method but using spray method only the DBD plasma treated samples displayed antimicrobial activity (log reduction of 5). Despite the better distribution achieved using ethanol as a solvent, water dispersion samples with DBD plasma treatment displayed better antimicrobial activity against S. aureus bacteria in both exhaustion (log reduction of 1.9) and spray (methods log reduction of 1.6) due to the different oxidation states of PA66 surface interacting with PVP-AgNPs, as demonstrated by X-Ray Photoelectron Spectroscopy (XPS) analysis. Spray method using the water-suspended PVP-AgNPs onto DBD plasma-treated samples is much faster, less agglomerating and uses 10 times less PVP-AgNPs dispersion than the exhaustion method to obtain an antimicrobial effect in both S. aureus and E. coli.

Atmospheric Pressure Plasma Deposition of Organosilicon Thin Films by Direct Current and Radio-frequency Plasma Jets.

Thin film deposition with atmospheric pressure plasmas is highly interesting for industrial demands and scientific interests in the field of biomaterials. However, the engineering of high-quality films by high-pressure plasmas with precise control over morphology and surface chemistry still poses a challenge. The two types of atmospheric-pressure plasma depositions of organosilicon films by the direct and indirect injection of hexamethyldisiloxane (HMDSO) precursor into a plasma region were chosen and compared in terms of the films chemical composition and morphology to address this. Although different methods of plasma excitation were used, the deposition of inorganic films with above 98% of SiO2 content was achieved for both cases. The chemical structure of the films was insignificantly dependent on the substrate type. The deposition in the afterglow of the DC discharge resulted in a soft film with high roughness, whereas RF plasma deposition led to a smoother film. In the case of the RF plasma deposition on polymeric materials resulted in films with delamination and cracks formation. Lastly, despite some material limitations, both deposition methods demonstrated significant potential for SiOx thin-films preparation for a variety of bio-related substrates, including glass, ceramics, metals, and polymers.

Plasma Processing with Fluorine Chemistry for Modification of Surfaces Wettability.

Using plasma in conjunction with fluorinated compounds is widely encountered in material processing. We discuss several plasma techniques for surface fluorination: deposition of fluorocarbon thin films either by magnetron sputtering of polytetrafluoroethylene targets, or by plasma-assisted chemical vapor deposition using tetrafluoroethane as a precursor, and modification of carbon nanowalls by plasma treatment in a sulphur hexafluoride environment. We showed that conformal fluorinated thin films can be obtained and, according to the initial surface properties, superhydrophobic surfaces can be achieved.