A New Method for Tungsten Oxide Nanopowder Deposition on Carbon-Fiber-Reinforced Polymer Composites for X-ray Attenuation.

A new method for the synthesis and deposition of tungsten oxide nanopowders directly on the surface of a carbon-fiber-reinforced polymer composite (CFRP) is presented. The CFRP was chosen because this material has very good thermal and mechanical properties and chemical resistance. Also, CFRPs have low melting points and are transparent under ionized radiation. The synthesis is based on the direct interaction between high-power-density microwaves and metallic wires to generate a high-temperature plasma in an oxygen-containing atmosphere, which afterward condenses as metallic oxide nanoparticles on the CFRP. During microwave discharge, the value of the electronic temperature of the plasma, estimated from Boltzmann plots, reached up to 4 eV, and tungsten oxide crystals with a size between 5 nm and 100 nm were obtained. Transmission electron microscopy (TEM) analysis of the tungsten oxide nanoparticles showed they were single crystals without any extended defects. Scanning electron microscopy (SEM) analysis showed that the surface of the CFRP sample does not degrade during microwave plasma deposition. The X-ray attenuation of CFRP samples covered with tungsten oxide nanopowder layers of 2 µm and 21 µm thickness was measured. The X-ray attenuation analysis indicated that the thin film with 2 µm thickness attenuated 10% of the photon flux with 20 to 29 KeV of energy, while the sample with 21 µm thickness attenuated 60% of the photon flux.

Mathematical formalism of femtosecond laser-deoxyribonucleic acid interaction: thermal evolution.

A novel analytical formalism is proposed based upon Quantum heat transport equation in order to describe the femtoseconds/picoseconds laser pulses interaction with the Deoxyribonucleic acid (DNA). The formalism generates solutions based upon inputs as: voltage, laser beam intensity and laser - DNA interaction time. Thermal waves induced inside irradiated DNA are defined and accounted for. Analytical simulations show that the optimum regime of laser - DNA interaction was reached for a potential carrier generated at the interface equal to 3.5 × 10-3 eV. It has to be mentioned that the formalism breaks down if the potential carrier generated at the interface is inferior to 10-2 eV. Accordingly, for pulse duration inferior to 1 ps, the laser beam spatial-temporal distribution has an essential role in defining the shape and magnitude of the thermal distribution within the irradiated DNA strands.

One-Temperature Analytical Model for Femto-/Atto-Second Laser-Metals Drilling: A Novel Approach.

Recently, ultrafast lasers have been developed and potentially become a point of interest worldwide, as their interaction with matter is yet unknown and can be mediated by new physical mechanisms. Real-time experimentation requires enormous costs, and there is therefore a need to develop computational models for this domain. By keeping in view this idea, a non-Fourier heat equation has solved the case of ultrafast laser-material interaction. Initial and boundary conditions were considered, and a one-dimensional mathematical model was presented. The simulations were compared with the experimental results for ultrashort laser-metallic sample interaction, and a close correlation was proven. It was found that the coupling of electron-phonon becomes "zero" due to short laser-material interaction time. The propagation of thermal waves was identified due to non-Fourier heat implementation. When the pulse duration increases, the variation in the thermal distribution becomes trivial due to an inverse correlation between the pulse duration and total energy within the pulse. When the laser-material interaction time decreases from fs to as, the generation of thermal waves increases and the powerful laser intensity acts as a shock wave during laser-material interaction, which causes a higher intensity of the thermal wave.

Nanostructured Fibers Containing Natural or Synthetic Bioactive Compounds in Wound Dressing Applications.

The interest in wound healing characteristics of bioactive constituents and therapeutic agents, especially natural compounds, is increasing because of their therapeutic properties, cost-effectiveness, and few adverse effects. Lately, nanocarriers as a drug delivery system have been actively investigated and applied in medical and therapeutic applications. In recent decades, researchers have investigated the incorporation of natural or synthetic substances into novel bioactive electrospun nanofibrous architectures produced by the electrospinning method for skin substitutes. Therefore, the development of nanotechnology in the area of dressings that could provide higher performance and a synergistic effect for wound healing is needed. Natural compounds with antimicrobial, antibacterial, and anti-inflammatory activity in combination with nanostructured fibers represent a future approach due to the increased wound healing process and regeneration of the lost tissue. This paper presents different approaches in producing electrospun nanofibers, highlighting the electrospinning process used in fabricating innovative wound dressings that are able to release natural and/or synthetic substances in a controlled way, thus enhancing the healing process.

Biomimetic Collagen/Zn2+-Substituted Calcium Phosphate Composite Coatings on Titanium Substrates as Prospective Bioactive Layer for Implants: A Comparative Study Spin Coating vs. MAPLE.

Synthesis of biomimetic materials for implants and prostheses is a hot topic in nanobiotechnology strategies. Today the major approach of orthopaedic implants in hard tissue engineering is represented by titanium implants. A comparative study of hybrid thin coatings deposition was performed by spin coating and matrix-assisted pulsed laser evaporation (MAPLE) onto titanium substrates. The Collagen-calcium phosphate (Coll-CaPs) combination was selected as the best option to mimic natural bone tissue. To accelerate the mineralization process, Zn2+ ions were inserted by substitution in CaPs. A superior thin film homogeneity was assessed by MAPLE, as shown by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) microscopy. A decrease of P-O and amide absorbance bands was observed as a consequence of different Zn2+ amounts. A variety of structural modifications of the apatite layer are then generated, which influenced the confinement process towards the collagen template. The in-vitro Simulated Body Fluid (SBF) assay demonstrated the ability of Coll/Zn2+-CaPs coatings to stimulate the mineralization process as a result of synergic effects in the collagen-Zn2+ substituted apatite. For both deposition methods, the formation of droplets associated to the growth of CaPs particulates inside the collagen matrix was visualized. This supports the prospective behavior of MAPLE biomimetic coatings to induce mineralization, as an essential step of fast implant integration with vivid tissues.

Synergistic effects of BMP-2, BMP-6 or BMP-7 with human plasma fibronectin onto hydroxyapatite coatings: A comparative study.

Design of new osteoinductive biomaterials to reproduce an optimized physiological environment capable of recruiting stem cells and instructing their fate towards the osteoblastic lineage has become a priority in orthopaedic surgery. This work aims at evaluating the bioactivity of BMP combined with human plasma fibronectin (FN/BMP) delivered in solution or coated onto titanium-hydroxyapatite (TiHA) surfaces. Herein, we focus on the comparison of in vitro osteogenic efficacy in mouse C2C12 pre-osteoblasts of three BMP members, namely: BMP-2, BMP-6 and BMP-7. In parallel, we evaluated the molecular binding strength between each BMP with FN using the Surface Plasmon Resonance (SPR) technology. The affinity of BMPs for FN was found totally different and dependent on BMP type. Indeed, the combination of FN with BMP-2 on TiHA surfaces potentiates the burst of gene-mediated osteogenic induction, while it prolongs the osteogenic activity of BMP-6 and surprisingly annihilates the BMP-7 one. These results correlate with FN/BMP affinity for TiHA, since BMP-6>BMP-2>BMP-7. In addition, by analyzing the osteogenic activity in the peri-implant environment, we showed that osteoinductive paracrine effects were significantly decreased upon (FN/BMP-6), as opposed to (FN/BMP-2) coatings. Altogether, our results support the use of FN/BMP-6 to develop a biomimetic microenvironment capable to induce osteogenic activity under physiological conditions, with minimum paracrine signalization. STATEMENT OF SIGNIFICANCE: The originality of our paper relies on the first direct comparison of the in vitro osteogenic potential of three osteogenic BMPs (BMP-2, -6 and -7) combined with native human plasma fibronectin delivered in solution or coated by laser transfer onto titanium hydroxyapatite surfaces. We confirm that BMP association with fibronectin enhances the osteogenic activity of BMP-2, -6 and -7, but with essential discrepancies, depending on the BMP member, and in agreement with the affinity of BMPs for fibronectin. Moreover, we bring elements to explain the origin of the BMP-2 medical life-threatening side-effects by analyzing in vitro paracrine effects. Finally, this work supports the alternative use of FN/BMP-6 to induce osteogenic activity under physiological conditions, with minimum side effects.

Functionalized Antimicrobial Composite Thin Films Printing for Stainless Steel Implant Coatings.

In this work we try to address the large interest existing nowadays in the better understanding of the interaction between microbial biofilms and metallic implants. Our aimed was to identify a new preventive strategy to control drug release, biofilm formation and contamination of medical devices with microbes. The transfer and printing of novel bioactive glass-polymer-antibiotic composites by Matrix-Assisted Pulsed Laser Evaporation into uniform thin films onto 316 L stainless steel substrates of the type used in implants are reported. The targets were prepared by freezing in liquid nitrogen mixtures containing polymer and antibiotic reinforced with bioglass powder. The cryogenic targets were submitted to multipulse evaporation by irradiation with an UV KrF* (λ = 248 nm, τFWHM ≤ 25 ns) excimer laser source. The prepared structures were analyzed by infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and profilometry, before and after immersion in physiological fluids. The bioactivity and the release of the antibiotic have been evaluated. We showed that the incorporated antibiotic underwent a gradually dissolution in physiological fluids thus supporting a high local treatment efficiency. Electrochemical measurements including linear sweep voltammetry and impedance spectroscopy studies were carried out to investigate the corrosion resistance of the coatings in physiological environments. The in vitro biocompatibility assay using the MG63 mammalian cell line revealed that the obtained nanostructured composite films are non-cytotoxic. The antimicrobial effect of the coatings was tested against Staphylococcus aureus and Escherichia coli strains, usually present in implant-associated infections. An anti-biofilm activity was evidenced, stronger against E. coli than the S. aureus strain. The results proved that the applied method allows for the fabrication of implantable biomaterials which shield metal ion release and possess increased biocompatibility and resistance to microbial colonization and biofilm growth.

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.

Antiresorption implant coatings based on calcium alendronate and octacalcium phosphate deposited by matrix assisted pulsed laser evaporation.

The integration of an implant material with bone tissue depends on the chemistry and physics of the implant surface. In this study we applied matrix assisted pulsed laser evaporation (MAPLE) in order to synthesize calcium alendronate monohydrate (a bisphosphonate obtained by calcium sequestration from octacalcium phosphate by alendronate) and calcium alendronate monohydrate/octacalcium phosphate composite thin films on titanium substrates. Octacalcium phosphate coatings were prepared as reference material. The powders, which were synthesized in aqueous medium, were suspended in deionised water, frozen at liquid nitrogen temperature and used as targets for MAPLE experiments. The transfer was conducted with a KrF* excimer laser source (λ = 248 nm, τFWHM ≤ 25 ns) in mild conditions of temperature and pressure. XRD, FTIR and SEM analyses confirmed that the coatings contain the same crystalline phases as the as-prepared powder samples. Osteoblast derived from stem cells and osteoclast derived from monocytes of osteoporotic subjects were co-cultured on the coatings up to 14 days. Osteoclast displayed significantly reduced proliferation and differentiation in the presence of calcium alendronate monohydrate, pointing to a clear role of the coatings containing this bisphosphonate on inhibiting excessive bone resorption. At variance, osteoblast production of alkaline phosphatase and type I pro-collagen were promoted by the presence of bisphosphonate, which also decreased the production of interleukin 6. The positive influence towards osteoblast differentiation was even more enhanced in the composite coatings, thanks to the presence of octacalcium phosphate.