Laser deposition of poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) - lysozyme microspheres based coatings with anti-microbial properties.

The purpose of this study was to obtain, characterize and evaluate the cytotoxicity and antimicrobial activity of coatings based on poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) - Lysozyme (P(3HB-3HV)/Lys) and P(3HB-3HV) - Polyethylene glycol - Lysozyme (P(3HB-3HV)/PEG/Lys) spheres prepared by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique, in order to obtain functional and improved Ti-based implants. Morphological investigation of the coatings by Infrared Microscopy (IRM) and SEM revealed that the average diameter of P(3HB-3HV)/Lys spheres is around 2µm and unlike the drop cast samples, IRM recorded on MAPLE films revealed a good distribution of monitored functional groups on the entire scanned surface. The biological evaluation of MAPLE structured surfaces revealed an improved biocompatibility with respect to osteoblasts and endothelial cells as compared with Ti substrates and an enhanced anti-biofilm effect against Gram positive (Staphylococcus aureus) and Gram negative (Pseudomonas aeruginosa) tested strains. Thus, we propose that the fabricated P(3HB-3HV)/PEG/Lys and P(3HB-3HV)/Lys microspheres may be efficiently used as a matrix for controlled local drug delivery, with practical applications in developing improved medical surfaces for the reduction of implant-associated infections.

Combinatorial MAPLE deposition of antimicrobial orthopedic maps fabricated from chitosan and biomimetic apatite powders.

Chitosan/biomimetic apatite thin films were grown in mild conditions of temperature and pressure by Combinatorial Matrix-Assisted Pulsed Laser Evaporation on Ti, Si or glass substrates. Compositional gradients were obtained by simultaneous laser vaporization of the two distinct material targets. A KrF* excimer (λ=248nm, τFWHM=25ns) laser source was used in all experiments. The nature and surface composition of deposited materials and the spatial distribution of constituents were studied by SEM, EDS, AFM, GIXRD, FTIR, micro-Raman, and XPS. The antimicrobial efficiency of the chitosan/biomimetic apatite layers against Staphylococcus aureus and Escherichia coli strains was interrogated by viable cell count assay. The obtained thin films were XRD amorphous and exhibited a morphology characteristic to the laser deposited structures composed of nanometric round shaped grains. The surface roughness has progressively increased with chitosan concentration. FTIR, EDS and XPS analyses indicated that the composition of the BmAp-CHT C-MAPLE composite films gradually modified from pure apatite to chitosan. The bioevaluation tests indicated that S. aureus biofilm is more susceptible to the action of chitosan-rich areas of the films, whilst the E. coli biofilm proved more sensible to areas containing less chitosan. The best compromise should therefore go, in our opinion, to zones with intermediate-to-high chitosan concentration which can assure a large spectrum of antimicrobial protection concomitantly with a significant enhancement of osseointegration, favored by the presence of biomimetic hydroxyapatite.

Structural, compositional, mechanical characterization and biological assessment of bovine-derived hydroxyapatite coatings reinforced with MgF2 or MgO for implants functionalization.

Hydroxyapatite (HA) is a consecrated biomaterial for bone reconstruction. In the form of thin films deposited by pulsed laser technologies, it can be used to cover metallic implants aiming to increase biocompatibility and osseointegration rate. HA of animal origin (bovine, BHA) reinforced with MgF2 (2wt.%) or MgO (5wt.%) were used for deposition of thin coatings with improved adherence, biocompatibility and antimicrobial activity. For pulsed laser deposition experiments, a KrF* (λ=248nm, τFWHM≤25ns) excimer laser source was used. The deposited structures were characterized from a physical-chemical point of view by X-Ray Diffraction, Fourier Transform Infra-Red Spectroscopy, Scanning Electron Microscopy in top- and cross-view modes, Energy Dispersive X-Ray Spectroscopy and Pull-out adherence tests. The microbiological assay using the HEp-2 cell line revealed that all target materials and deposited thin films are non-cytotoxic. We conducted tests on three strains isolated from patients with dental implants failure, i.e. Microccocus sp., Enterobacter sp. and Candida albicans sp. The most significant anti-biofilm effect against Microcococcus sp. strain, at 72h, was obtained in the presence of BHA:MgO thin films. For Enterobacter sp. strain a superior antimicrobial activity at 72h was noticed, in respect with simple BHA or Ti control. The enhanced antimicrobial performances, correlated with good cytocompatibility and mechanical properties recommend these biomaterials as an alternative to synthetic HA for the fabrication of reliable implant coatings for dentistry and other applications.

Electrical, structural, and optical properties of sulfurized Sn-doped In2O 3 nanowires.

Sn-doped In2O3 nanowires have been grown on Si via the vapor-liquid-solid mechanism at 800 °C and then exposed to H2S between 300 to 600 °C. We observe the existence of cubic bixbyite In2O3 and hexagonal SnS2 after processing the Sn:In2O3 nanowires to H2S at 300 °C but also cubic bixbyite In2O3, which remains dominant, and the emergence of rhombohedral In2(SO4)3 at 400 °C. The resultant nanowires maintain their metallic-like conductivity, and exhibit photoluminescence at 3.4 eV corresponding to band edge emission from In2O3. In contrast, Sn:In2O3 nanowires grown on glass at 500 °C can be treated under H2S only below 200 °C which is important for the fabrication of Cu2S/Sn:In2O3 core-shell p-n junctions on low-cost transparent substrates such as glass suitable for quantum dot-sensitized solar cells.

Structural and biological evaluation of lignin addition to simple and silver-doped hydroxyapatite thin films synthesized by matrix-assisted pulsed laser evaporation.

We report on thin film deposition by matrix-assisted pulsed laser evaporation of simple hydroxyapatite (HA) or silver (Ag) doped HA combined with the natural biopolymer organosolv lignin (Lig) (Ag:HA-Lig). Solid cryogenic target of aqueous dispersions of Ag:HA-Lig composite and its counterpart without silver (HA-Lig) were prepared for evaporation using a KrF* excimer laser source. The expulsed material was assembled onto TiO2/Ti substrata or silicon wafers and subjected to physical-chemical investigations. Smooth, uniform films adherent to substratum were observed. The chemical analyses confirmed the presence of the HA components, but also evidenced traces of Ag and Lig. Deposited HA was Ca deficient, which is indicative of a film with increased solubility. Recorded X-ray Diffraction patterns were characteristic for amorphous films. Lig presence in thin films was undoubtedly proved by both X-ray Photoelectron and Fourier Transform Infra-Red Spectroscopy analyses. The microbiological evaluation showed that the newly assembled surfaces exhibited an inhibitory activity both on the initial steps of biofilm forming, and on mature bacterial and fungal biofilm development. The intensity of the anti-biofilm activity was positively influenced by the presence of the Lig and/or Ag, in the case of Staphylococcus aureus, Pseudomonas aeruginosa and Candida famata biofilms. The obtained surfaces exhibited a low cytotoxicity toward human mesenchymal stem cells, being therefore promising candidates for fabricating implantable biomaterials with increased biocompatibility and resistance to microbial colonization and further biofilm development.

Iron oxide-based nanoparticles with different mean sizes obtained by the laser pyrolysis: structural and magnetic properties.

Nano-sized iron oxide-based particles have been directly synthesized by the laser induced pyrolysis of a mixture containing iron pentacarbonyl/air (as oxidizer)/ethylene (as sensitizer). In this paper we further demonstrate the possibility to vary the chemical composition and the nanoparticle dimensions of the iron oxide-based materials by handling the oxidation procedure in the frame of the laser pyrolysis process. Thus, nanoparticles with major maghemite/magnetite content may change composition into mixtures with variable amounts of three components: major gamma-Fe2O3/Fe3O4 iron oxide, metallic Fe and cementite Fe3C. By X-ray diffraction (XRD) it is found that the relative proportion of these phases differs in function of the reaction temperature (laser power). As revealed by transmission electron microscopy (TEM), mean particle sizes between about 4 nm and 6 nm and between about 9 and 11 nm may be prepared by varying the oxidation procedure and the laser power, respectively. By the controlled heating of samples (maximum temperature 185 degrees C), increased crystallinity for the gamma-Fe2O3/Fe3O4 oxide phase was found as well as an increase of the mean particle diameters. The examination of the magnetization curves for samples obtained for different laser powers indicates notable differences in the magnetic behavior and parameters. The temperature dependent Mossbauer measurements confirm the formation of larger particles at higher laser power densities as well as the presence of inter-particle magnetic interactions. On this basis, the estimation of phase composition for the different representative samples is given.