One-step preparation of nitrogen doped titanium oxide/Au/reduced graphene oxide composite thin films for photocatalytic applications

© The Royal Society of Chemistry 2015. Titanium dioxide (TiO2) and TiO2/Au/reduced graphene oxide (rGO) nanocomposite thin films were grown by ultraviolet matrix assisted pulsed laser evaporation (UV-MAPLE) in controlled O2 or N2 atmospheres. An UV KrF∗ excimer laser (λ = 248 nm, τFWHM ∼ 25 ns, ν = 10 Hz) was used for the irradiation of the MAPLE targets consisting of TiO2 nanoparticles (NPs) or mixtures of TiO2 NPs, Au NPs, and graphene oxide (GO) platelets in aqueous solutions. The effect of Au and GO addition as well as nitrogen doping on the photocatalytic activity of the TiO2 thin films was investigated. The evaluation of the photocatalytic activity was performed by photodegradation of the organic methylene blue model dye pollutant under UV-visible light, >simulated sun> irradiation conditions. Our results show that the photocatalytic properties of TiO2 were significantly improved by the addition of Au NPs and rGO platelets. Nitrogen inclusion into the rGO structure further contributes to the enhancement of the TiO2/Au/rGO nanocomposites photocatalytic activity.The authors thank the financial support of the Executive Unit for Financing Higher Education, Research, Development, and Innovation of the Romanian Ministry of Education and Scientific Research under the contract PN-IIPT-PCCA-2011-3.2-1235 and the Spanish Ministry of Economy and Competitiveness under the contract ENE2014-56109-C3-3-R.Peer reviewedPeer Reviewe

Biomimetic nanocrystalline apatite coatings synthesized by Matrix Assisted Pulsed Laser Evaporation for medical applications

tWe report the deposition by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique of biomimeticnanocrystalline apatite coatings on titanium substrates, with potential application in tissue engineering.The targets were prepared from metastable, nanometric, poorly crystalline apatite powders, analogousto mineral bone, synthesized through a biomimetic approach by double decomposition process. For thedeposition of thin films, a KrF* excimer laser source was used (λ = 248 nm, τFWHM ≤ 25 ns). The analy-ses revealed the existence, in synthesized powders, of labile non-apatitic mineral ions, associated withthe formation of a hydrated layer at the surface of the nanocrystals. The thin film analyses showedthat the structural and chemical nature of the nanocrystalline apatite was prevalently preserved. Theperpetuation of the non-apatitic environments was also observed. The study indicated that MAPLE isa suitable technique for the congruent transfer of a delicate material, such as the biomimetic hydratednanohydroxyapatite

Pulsed Laser Deposition of Aluminum Nitride Films: Correlation between Mechanical, Optical, and Structural Properties

Aluminum nitride (AlN) films were synthesized onto Si(100) substrates by pulsed laser deposition (PLD) in vacuum or nitrogen, at 0.1, 1, 5, or 10 Pa, and substrate temperatures ranging from RT to 800 °C. The laser parameters were set at: incident laser fluence of 3–10 J/cm2 and laser pulse repetition frequency of 3, 10, or 40 Hz, respectively. The films’ hardness was investigated by depth-sensing nanoindentation. The optical properties were studied by FTIR spectroscopy and UV-near IR ellipsometry. Hardness values within the range of 22–30 GPa and Young’s modulus values of 230–280 GPa have been inferred. These values were determined by the AlN film structure that consisted of nanocrystallite grains, strongly dependent on the deposition parameters. The values of optical constants, superior to amorphous AlN, support the presence of crystallites in the amorphous film matrix. They were visualized by TEM and evidenced by FTIR spectroscopy. The characteristic Reststrahlen band of the h-AlN lattice with component lines arising from IR active phonon vibrational modes in AlN nanocrystallites was well detectable within the spectral range of 950–500 cm−1. Control X-ray diffraction and atomic force microscopy data were introduced and discussed. All measurements delivered congruent results and have clearly shown a correlation between the films’ structure and the mechanical and optical properties dependent on the experimental conditions

In Vivo Assessment of Bone Enhancement in the Case of 3D-Printed Implants Functionalized with Lithium-Doped Biological-Derived Hydroxyapatite Coatings: A Preliminary Study on Rabbits

We report on biological-derived hydroxyapatite (HA, of animal bone origin) doped with lithium carbonate (Li-C) and phosphate (Li-P) coatings synthesized by pulsed laser deposition (PLD) onto Ti6Al4V implants, fabricated by the additive manufacturing (AM) technique. After being previously validated by in vitro cytotoxicity tests, the Li-C and Li-P coatings synthesized onto 3D Ti implants were preliminarily investigated in vivo, by insertion into rabbits’ femoral condyles. The in vivo experimental model for testing the extraction force of 3D metallic implants was used for this study. After four and nine weeks of implantation, all structures were mechanically removed from bones, by tensile pull-out tests, and coatings’ surfaces were investigated by scanning electron microscopy. The inferred values of the extraction force corresponding to functionalized 3D implants were compared with controls. The obtained results demonstrated significant and highly significant improvement of functionalized implants’ attachment to bone (p-values ≤0.05 and ≤0.00001), with respect to controls. The correct placement and a good integration of all 3D-printed Ti implants into the surrounding bone was demonstrated by performing computed tomography scans. This is the first report in the dedicated literature on the in vivo assessment of Li-C and Li-P coatings synthesized by PLD onto Ti implants fabricated by the AM technique. Their improved mechanical characteristics, along with a low fabrication cost from natural, sustainable resources, should recommend lithium-doped biological-derived materials as viable substitutes of synthetic HA for the fabrication of a new generation of metallic implant coatings

In Vivo Assessment of Synthetic and Biological-Derived Calcium Phosphate-Based Coatings Fabricated by Pulsed Laser Deposition: A Review

The aim of this review is to present the state-of-the art achievements reported in the last two decades in the field of pulsed laser deposition (PLD) of biocompatible calcium phosphate (CaP)-based coatings for medical implants, with an emphasis on their in vivo biological performances. There are studies in the dedicated literature on the in vivo testing of CaP-based coatings (especially hydroxyapatite, HA) synthesized by many physical vapor deposition methods, but only a few of them addressed the PLD technique. Therefore, a brief description of the PLD technique, along with some information on the currently used substrates for the synthesis of CaP-based structures, and a short presentation of the advantages of using various animal and human implant models will be provided. For an in-depth in vivo assessment of both synthetic and biological-derived CaP-based PLD coatings, a special attention will be dedicated to the results obtained by standardized and micro-radiographies, (micro) computed tomography and histomorphometry, tomodensitometry, histology, scanning and transmission electron microscopies, and mechanical testing. One main specific result of the in vivo analyzed studies is related to the demonstrated superior osseointegration characteristics of the metallic (generally Ti) implants functionalized with CaP-based coatings when compared to simple (control) Ti ones, which are considered as the “gold standard” for implantological applications. Thus, all such important in vivo outcomes were gathered, compiled and thoroughly discussed both to clearly understand the current status of this research domain, and to be able to advance perspectives of these synthetic and biological-derived CaP coatings for future clinical applications

A Review on Biphasic Calcium Phosphate Materials Derived from Fish Discards

This review summarizes the results reported on the production of biphasic calcium phosphate (BCP) materials derived from fish wastes (i.e., heads, bones, skins, and viscera), known as fish discards, and offers an in-depth discussion on their promising potential for various applications in many fields, especially the biomedical one. Thus, considerable scientific and technological efforts were recently focused on the capability of these sustainable materials to be transformed into economically attractive and highly valuable by-products. As a consequence of using these wastes, plenty of beneficial social effects, with both economic and environmental impact, will arise. In the biomedical field, there is a strong and continuous interest for the development of innovative solutions for healthcare improvement using alternative materials of biogenic origin. Thus, the orthopedic field has witnessed a significant development due to an increased demand for a large variety of implants, grafts, and/or scaffolds. This is mainly due to the increase of life expectancy and higher frequency of bone-associated injuries and diseases. As a consequence, the domain of bone-tissue engineering has expanded to be able to address a plethora of bone-related traumas and to deliver a viable and efficient substitute to allografts or autografts by combining bioactive materials and cells for bone-tissue ingrowth. Among biomaterials, calcium phosphate (CaP)-based bio-ceramics are widely used in medicine, in particular in orthopedics and dentistry, due to their excellent bioactive, osteoconductive, and osteointegrative characteristics. Recently, BCP materials (synthetic or natural), a class of CaP, which consist of a mixture of two phases, hydroxyapatite (HA) and beta tricalcium phosphate (β-TCP), in different concentrations, gained increased attention due to their superior overall performances as compared to single-phase formulations. Moreover, the exploitation of BCP materials from by-products of fish industry was reported to be a safe, cheap, and simple procedure. In the dedicated literature, there are many reviews on synthetic HA, β-TCP, or BCP materials, but to the best of our knowledge, this is the first collection of results on the effects of processing conditions on the morphological, compositional, structural, mechanical, and biological properties of the fish discard-derived BCPs along with the tailoring of their features for various applications

Advances and Challenges in Pulsed Laser Deposition for Complex Material Applications

Various physical vapor deposition (PVD) techniques, such as molecular beam epitaxy, electron beam physical vapor deposition, pulsed laser deposition (PLD), arc discharge, magnetron sputtering and/or ion beam sputtering, are currently used for coating or growing thin films on solid substrates [...

Current Status on Pulsed Laser Deposition of Coatings from Animal-Origin Calcium Phosphate Sources

The aim of this paper is to present the current status on animal-origin hydroxyapatite (HA) coatings synthesized by Pulsed Laser Deposition (PLD) technique for medical implant applications. PLD as a thin film synthesis method, although limited in terms of surface covered area, still gathers interest among researchers due to its advantages such as stoichiometric transfer, thickness control, film adherence, and relatively simple experimental set-up. While animal-origin HA synthesized by bacteria or extracted from animal bones, eggshells, and clams was tested in the form of thin films or scaffolds as a bioactive agent before, the reported results on PLD coatings from HA materials extracted from natural sources were not gathered and compared until the present study. Since natural apatite contains trace elements and new functional groups, such as CO32− and HPO42− in its complex molecules, physical-chemical results on the transfer of animal-origin HA by PLD are extremely interesting due to the stoichiometric transfer possibilities of this technique. The points of interest of this paper are the origin of HA from various sustainable resources, the extraction methods employed, the supplemental functional groups, and ions present in animal-origin HA targets and coatings as compared to synthetic HA, the coatings’ morphology function of the type of HA, and the structure and crystalline status after deposition (where properties were superior to synthetic HA), and the influence of various dopants on these properties. The most interesting studies published in the last decade in scientific literature were compared and morphological, elemental, structural, and mechanical data were compiled and interpreted. The biological response of different types of animal-origin apatites on a variety of cell types was qualitatively assessed by comparing MTS assay data of various studies, where the testing conditions were possible. Antibacterial and antifungal activity of some doped animal-origin HA coatings was also discussed

Advances and Challenges in Pulsed Laser Deposition for Complex Material Applications

Various physical vapor deposition (PVD) techniques, such as molecular beam epitaxy, electron beam physical vapor deposition, pulsed laser deposition (PLD), arc discharge, magnetron sputtering and/or ion beam sputtering, are currently used for coating or growing thin films on solid substrates [...