Cellulose Nanocrystals as Additives in Electrospun Biocompatible Separators for Aprotic Lithium-Ion Batteries.

This work concerns the study of electrospun scaffolds as separators for aprotic lithium-ion batteries (LIBs) composed of the amorphous poly-d,l-lactide (PDLLA), in solution concentrations of 8, 10, and 12 wt % and in different ratios with cellulose nanocrystals (CNCs). PDLLA has been studied for the first time as a separator, taking into account its amorphous character that could facilitate electrolyte incorporation into the polymer matrix and influence ionic conductivity, together with CNCs, for reducing the hydrophobicity of the scaffolds. The embedding of the nanocrystals in the scaffolds was confirmed by X-ray diffraction analysis and attenuated total reflectance Fourier transform infrared spectroscopy. The polymer combination influenced the nanofibrous morphology as evaluated by scanning electron microscopy and modulated the electrochemical behavior of the membranes that was investigated through linear sweep voltammetry, cyclic voltammetry, and electrochemical impedance spectroscopy tests. Among the studied categories, the P12 series displayed a nonhomogeneous electrolyte resistance and electrochemical stability, differently from P10, whose results suggested their application in LIBs with standard formulation, as confirmed by a preliminary performance test of the P10N6 formulation in a full Li-ion cell configuration.

Antimicrobial Cu-Doped TiO2 Coatings on the ß Ti-30Nb-5Mo Alloy by Micro-Arc Oxidation.

Among the different surface modification techniques, micro-arc oxidation (MAO) is explored for its ability to enhance the surface properties of Ti alloys by creating a controlled and durable oxide layer. The incorporation of Cu ions during the MAO process introduces additional functionalities to the surface, offering improved corrosion resistance and antimicrobial activity. In this study, the ß-metastable Ti-30Nb-5Mo alloy was oxidated through the MAO method to create a Cu-doped TiO2 coating. The quantity of Cu ions in the electrolyte was changed (1.5, 2.5, and 3.5 mMol) to develop coatings with different Cu concentrations. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron and atomic force microscopies, contact angle, and Vickers microhardness techniques were applied to characterize the deposited coatings. Cu incorporation increased the antimicrobial activity of the coatings, inhibiting the growth of Staphylococcus aureus, Enterococcus faecalis, Pseudomonas aeruginosa bacteria strains, and Candida albicans fungus by approximately 44%, 37%, 19%, and 41%, respectively. Meanwhile, the presence of Cu did not inhibit the growth of Escherichia coli. The hardness of all the deposited coatings was between 4 and 5 GPa. All the coatings were non-cytotoxic for adipose tissue-derived mesenchymal stem cells (AMSC), promoting approximately 90% of cell growth and not affecting the AMSC differentiation into the osteogenic lineage.

LIPSS Applied to Wide Bandgap Semiconductors and Dielectrics: Assessment and Future Perspectives.

With the aim of presenting the processes governing the Laser-Induced Periodic Surface Structures (LIPSS), its main theoretical models have been reported. More emphasis is given to those suitable for clarifying the experimental structures observed on the surface of wide bandgap semiconductors (WBS) and dielectric materials. The role played by radiation surface electromagnetic waves as well as Surface Plasmon Polaritons in determining both Low and High Spatial Frequency LIPSS is briefly discussed, together with some experimental evidence. Non-conventional techniques for LIPSS formation are concisely introduced to point out the high technical possibility of enhancing the homogeneity of surface structures as well as tuning the electronic properties driven by point defects induced in WBS. Among these, double- or multiple-fs-pulse irradiations are shown to be suitable for providing further insight into the LIPSS process together with fine control on the formed surface structures. Modifications occurring by LIPSS on surfaces of WBS and dielectrics display high potentialities for their cross-cutting technological features and wide applications in which the main surface and electronic properties can be engineered. By these assessments, the employment of such nanostructured materials in innovative devices could be envisaged.

Laser Irradiation of a Bio-Waste Derived Carbon Unlocks Performance Enhancement in Secondary Lithium Batteries.

Pyrolyzed carbons from bio-waste sources are renewable nanomaterials for sustainable negative electrodes in Li- and Na-ion batteries. Here, carbon derived from a hazelnut shell has been obtained by hydrothermal processing of the bio-waste followed by thermal treatments and laser irradiation in liquid. A non-focused nanosecond pulsed laser source has been used to irradiate pyrolyzed carbon particles suspended in acetonitrile to modify the surface and morphology. Morphological, structural, and compositional changes have been investigated by microscopy, spectroscopy, and diffraction to compare the materials properties after thermal treatments as well as before and after the irradiation. Laser irradiation in acetonitrile induces remarkable alteration in the nanomorphology, increase in the surface area and nitrogen enrichment of the carbon surfaces. These materials alterations are beneficial for the electrochemical performance in lithium half cells as proved by galvanostatic cycling at room temperature.

Manganese-containing Bioactive Glass Enhances Osteogenic Activity of TiO2 Nanotube Arrays.

Titanium and its alloys are the most used biomaterials for orthopedic and dental applications. However, up to 10% of these medical devices still fail, mostly due to implant loosening and suboptimal integration at the implant site. The biomaterial surface plays a critical role in promoting osseointegration, which can reduce the risk of device failure. In this study, we propose a novel surface modification on titanium to improve osteogenic differentiation by depositing manganese-containing bioactive glass (BG) on TiO2 nanotube arrays. The surfaces were characterized by scanning electron microscopy, energy dispersive X-ray spectrometer, contact angle goniometry, and X-ray photoelectron spectroscopy. Cell toxicity, viability, adhesion, and proliferation of adipose-derived stem cells on the surfaces were investigated up to 7 days. To evaluate the osteogenic properties of the surfaces, alkaline phosphatase activity, total protein, osteocalcin expression, and calcium deposition were quantified up to 28 days. The results indicate that TiO2 nanotube arrays modified with BG promote cell growth and induce increased osteocalcin and calcium contents when compared to unmodified TiO2 nanotube arrays. The deposition of manganese-containing bioactive glass onto TiO2 nanotubes demonstrates the ability to enhance osteogenic activity on titanium, showing great potential for use in orthopedic and dental implants.

Removal of diclofenac from aqueous solutions by adsorption on thermo-plasma expanded graphite.

The adsorption of diclofenac on thermo-plasma expanded graphite (a commercial product) from water solutions was investigated. The adsorbent material was characterized by SEM, TEM, BET, Raman and X-ray diffraction analyses. Typical diffractogram and Raman spectrum of graphitic material, dimension of 24.02 nm as crystallite dimension and a surface area of 47 m2 g-1 were obtained. The effect of pH on the adsorption capacity was evaluated in the range 1-7 and the adsorption mechanism was described by kinetic and isothermal studies. Pseudo-second order and Dubinin-Radushkevich models agreed with theoretical values of adsorption capacity (i.e. 400 and 433 mg g-1, respectively) and resulted to be the best fit for kinetics and isothermal experimental data. The thermodynamics of the process was evaluated by plotting the adsorption capacity/concentration ratio at the equilibrium as a function of different values of the multiplicative inverse of temperature. Moreover, the adsorbent regeneration was also investigated, comparing two different remediation techniques. Solvent washing performed with NaOH 0.2 M and thermo-treatment carried out by heating in an oven at 105 °C for 2 h and then at 200 °C for 4 h. The thermo-treatment was the best technique to regenerate the adsorbent, ensuring same performance after 4 cycles of use and regeneration.

Pulsed laser deposition temperature effects on strontium-substituted hydroxyapatite thin films for biomedical implants.

Substituting small molecule drugs with abundant and easily affordable ions may have positive effects on the way countless disease treatments are approached. The interest in strontium cation in bone therapies soared in the wake of the success of strontium ranelate in the treatment of osteoporosis. A new method for producing thin strontium-containing hydroxyapatite (Sr-HA, Ca9Sr(PO4)6(OH)2) films as coatings that render bioinert titanium implant bioactive is reported here. The method is based on the combination of a mechanochemical synthesis of Sr-HA targets and their deposition in form of thin films on top of titanium with the use of laser ablation at low pressure. The films were 1-2 µm in thickness and their formation was studied at different temperatures, including 25, 300, and 500 °C. Highly crystalline Sr-HA target transformed during pulsed laser deposition to a fully amorphous film, whose degree of long-range order recovered with temperature. Particle edges became somewhat sharper and surface roughness moderately increased with temperature, but the (Ca+Sr)/P atomic ratio, which increased 1.5 times during the film formation, remained approximately constant at different temperatures. Despite the mostly amorphous structure of the coatings, their affinity for capturing atmospheric carbon dioxide and accommodating it as carbonate ions that replace both phosphates and hydroxyls of HA was confirmed in an X-ray photoelectron spectroscopic analysis. As the film deposition temperature increased, the lattice voids got reduced in concentration and the structure gradually "closed," becoming more compact and entailing a linear increase in microhardness with temperature, by 0.03 GPa/°C for the entire 25-500 °C range. Biocompatibility and bioactivity of Sr-HA thin films deposited on titanium were confirmed in an interaction with dental pulp stem cells, suggesting that these coatings, regardless of the processing temperature, may be viable candidates for the surface components of metallic bone implants.

Transition Metal Carbide Core/Shell Nanoparticles by Ultra-Short Laser Ablation in Liquid.

Transition metal carbide nanoparticles are a class of technological interesting materials with a wide range of applications. Among metal carbides, tantalum carbides have good compatibility with the biological environment while molybdenum carbides are used as catalyst in electrochemical reactions. Laser ablation of bulk transition metal targets in some liquids is here reported and laser ablation in organic solvents is used as simple synthetic strategy for the production of carbide nanostructures. Herein, the nanoparticles produced by ultra-short laser ablation of tantalum and molybdenum in water, acetone, ethanol and toluene have been characterized by TEM, XRD and XPS analysis. The combined effect of metal and solvent chemical and physical properties on the composition of the nanomaterials obtained has been pointed out. In particular, the different reactivity of Ta and Mo with respect to oxidizing species determines the composition of particles obtained in water, on the other hand the organic solvents decomposition allows to obtain transition metal carbide (TMC) nanoparticles. The observed carbonaceous shell formed on TMC allows to protect the particle's carbidic core and to improve and tailor the applications of these nanomaterials.

Cu-Releasing Bioactive Glass Coatings and Their in Vitro Properties.

Bioactive glasses are well-known materials suitable for bone-related applications thanks to their biocompatibility and osteoconductivity. In order to improve their in vivo performance, the modification of the glass composition by adding ions with specific biological functions is required. As copper (Cu) possesses antibacterial properties, in this study, 5 wt % of CuO has been added to the 45S5 bioactive glass composition. The investigation of the effect of the Cu-containing bioactive glass on cellular behavior has revealed that the presence of Cu induces an early differentiation of human mesenchymal stem cells through osteoblast phenotype, promotes the expression of anti-inflammatory interleukin, and reduces proinflammatory interleukin expression. With the aim to produce coatings with antibacterial properties, the Cu-containing bioactive glass was used as the target material for the pulsed laser deposition (PLD) of bioactive thin films. PLD experiments were carried out at different substrate temperatures to study the effect on the film's characteristics. All of the films are compact, crack-free, and characterized by a rough morphology and good wettability. The in vitro bioactivity was demonstrated by the apatite growth on the coating surface, after soaking in simulated body fluid, revealed by Raman spectroscopy and scanning electron microscopy-energy dispersive X-ray analyses. The antibacterial study proved that the material showed more effective activity against three Gram-negative bacteria ( Pseudomonas aeruginosa, Escherichia coli, Salmonella enterica) rather than against Gram-positive bacteria ( Staphylococcus aureus).

Silica Xerogel Obtained by Ultrashort Laser Irradiation of Tetraethyl Orthosilicate.

The formation of an opaque solid foam was induced by the direct interaction between tetraethyl orthosilicate (TEOS) and an ultrashort femtosecond laser source(Nd:glass, 527 nm, 10 Hz, 250 fs). The product, which resulted to be a silica xerogel, was characterized by different techniques. In particular, information about the morphology was obtained by scanning and transmission electron microscopy (SEM and TEM), while the presence of different functional groups was studied through IR measurements. Since the properties of this kind of material can be improved by functionalizing it with metal nanoparticles, a palladium metal target was ablated in liquid TEOS. TEM images show that palladium was present in the form of nanoparticles and EDX measurements confirm the presence of the metal inside the silica network.

Formation of Titanium Carbide (TiC) and TiC@C core-shell nanostructures by ultra-short laser ablation of titanium carbide and metallic titanium in liquid.

Laser ablation of bulk target in liquid allows to obtain stable nanoparticles and nanostructures, also in metastable phases, limiting the use of hazardous reagents and extreme reaction conditions. Titanium carbide (TiC) is a ceramic compound with several technological applications ranging from biocompatible materials to wear resistant coatings. The possibility to obtain core/shell structures expands its range of application due to the ability of modify the surface properties of the core ceramic material. TiC and metallic titanium targets have been ablated by means of an ultra-short laser source in different liquid media (water, acetone, n-hexane and toluene). The obtained colloidal solutions have been characterized by TEM, XRD and micro-Raman analysis. In all the used experimental conditions TiC nanoparticles have been produced. During water and acetone mediated ablations, the oxidation of titanium has been observed, whereas by using oxygen free solvents, such as n-hexane and toluene, core/shell TiC nanoparticles embedded in amorphous and graphitic carbon shell, respectively, have been obtained.

Placenta Derived Mesenchymal Stem Cells Hosted on RKKP Glass-Ceramic: A Tissue Engineering Strategy for Bone Regenerative Medicine Applications.

In tissue engineering protocols, the survival of transplanted stem cells is a limiting factor that could be overcome using a cell delivery matrix able to support cell proliferation and differentiation. With this aim, we studied the cell-friendly and biocompatible behavior of RKKP glass-ceramic coated Titanium (Ti) surface seeded with human amniotic mesenchymal stromal cells (hAMSCs) from placenta. The sol-gel synthesis procedure was used to prepare the RKKP glass-ceramic material, which was then deposited onto the Ti surface by Pulsed Laser Deposition method. The cell metabolic activity and proliferation rate, the cytoskeletal actin organization, and the cell cycle phase distribution in hAMSCs seeded on the RKKP coated Ti surface revealed no significant differences when compared to the cells grown on the treated plastic Petri dish. The health of of hAMSCs was also analysed studying the mRNA expressions of MSC key genes and the osteogenic commitment capability using qRT-PCR analysis which resulted in being unchanged in both substrates. In this study, the combination of the hAMSCs' properties together with the bioactive characteristics of RKKP glass-ceramics was investigated and the results obtained indicate its possible use as a new and interesting cell delivery system for bone tissue engineering and regenerative medicine applications.

Interdisciplinary approach to cell-biomaterial interactions: biocompatibility and cell friendly characteristics of RKKP glass-ceramic coatings on titanium.

In this work, titanium (Ti) supports have been coated with glass-ceramic films for possible applications as biomedical implant materials in regenerative medicine. For the film preparation, a pulsed laser deposition (PLD) technique has been applied. The RKKP glass-ceramic material, used for coating deposition, was a sol-gel derived target of the following composition: Ca-19.4, P-4.6, Si-17.2, O-43.5, Na-1.7, Mg-1.3, F-7.2, K-0.2, La-0.8, Ta-4.1 (all in wt%). The prepared coatings were compact and uniform, characterised by a nanometric average surface roughness. The biocompatibility and cell-friendly properties of the RKKP glass-ceramic material have been tested. Cell metabolic activity and proliferation of human colon carcinoma CaCo-2 cells seeded on RKKP films showed the same exponential trend found in the control plastic substrates. By the phalloidin fluorescence analysis, no significant modifications in the actin distribution were revealed in cells grown on RKKP films. Moreover, in these cells a high mRNA expression of markers involved in protein synthesis, proliferation and differentiation, such as villin (VIL1), alkaline phosphatase (ALP1), ß-actin (ß-ACT), Ki67 and RPL34, was recorded. In conclusion, the findings, for the first time, demonstrated that the RKKP glass-ceramic material allows the adhesion, growth and differentiation of the CaCo-2 cell line.

Superhard tungsten tetraboride films prepared by pulsed laser deposition method.

Attempts to synthesize and/or theoretically predict new superhard materials are the subject of an intense research activity. The trials to deposit them in the form of films have just began. WB(2) (77 wt % WB(2) and 23 wt % WB(4)) and WB(4) (65 wt % WB(4) and 35 wt % WB(2)) polycrystalline bulk samples were obtained in this work via electron beam synthesis technique and, subsequently, used as targets for films preparation by the pulsed laser deposition method. The targets were irradiated by a frequency-doubled Nd:glass laser with a pulse duration of 250 fs. The films grown on SiO(2) substrates at 600 °C were characterized by X-ray diffraction, scanning electron and atomic force microscopies, and Vickers microhardness technique. The deposited films are composed of WB(4). The intrinsic film hardness, calculated according to the "law-of-mixtures" model, lies in the superhardness region 42-50 GPa.

Superhard properties of rhodium and iridium boride films.

Very recently, the superhard properties of rhenium and ruthenium boride films were reported, this research being inspired by the discovery of the ReB(2) bulk superhardness. In this paper, we report the first successful deposition and characterization of rhodium and iridium boride films, other possible candidates for superhard materials. The films were prepared, applying the pulsed laser deposition technique, and studied by X-ray diffraction, scanning electron and atomic force microscopies, and Vickers microhardness. The refined structural parameters for RhB(1.1) and IrB(1.1) films were obtained. The RhB(1.1) film is characterized by the submicrometer crystallite size, whereas for the IrB(1.1) film, the crystallite size is in the tens of nanometers range, and this latter film presents a slightly preferred orientation along the [004] direction. Both the films exhibit very similar morphology, being composed of dense globular aggregate texture. The RhB(1.1) film presents a homogeneously textured surface with an average roughness of 20-50 nm, whereas the IrB(1.1) film possesses a finer texture with an average roughness of 20-30 nm. The intrinsic hardness of both films lies in the superhardness range: the 1.0 microm thick RhB(1.1) film possesses a hardness of 44 GPa, whereas the 0.4 microm thick IrB(1.1) film has a hardness of 43 GPa.

Nanoparticles and thin film formation in ultrashort pulsed laser deposition of vanadium oxide.

The ultrashort pulsed laser deposition of vanadium oxide thin films has been carried out by a frequency-doubled Nd:glass laser with a pulse duration of 250 fs. The characteristics of the plasma produced by the laser-target interaction have been studied by ICCD imaging and optical emission spectroscopy. The results confirm that an emitting plasma produced by ultrashort laser pulses is formed by both a primary and a secondary component. The secondary component consists of particles with a nanometric size, and their composition and spatial angular distribution influence the deposited films. In fact, these films, analyzed by X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, and atomic force microscopy, are formed by the aggregation of a large number of nanoparticles whose composition is explained by a model based on equilibrium thermal evaporation from particles directly ejected from the target. On these basis, the presence in the films of a mixture of V(2)O(5) and VO(2) is discussed.

Theoretical modeling of laser ablation of quaternary bronze alloys: case studies comparing femtosecond and nanosecond LIBS experimental data.

A model, formerly proposed and utilized to understand the formation of laser induced breakdown spectroscopy (LIBS) plasma upon irradiation with nanosecond laser pulses at different fluences and wavelengths, has been extended to the irradiation with femtosecond laser pulses in order to control the fractionation mechanisms which heavily affect the application of laser-ablation-based microanalytical techniques. The model takes into account the different chemico-physical processes occurring during the interaction of an ultrashort laser pulse with a metallic surface. In particular, a two-temperature description, relevant to the electrons and lattice of the substrate, respectively, has been introduced and applied to different ternary and quaternary copper-based alloys subjected to fs and ns ablation both in the visible (527 nm) and in the UV (248 nm). The model has been found able to reproduce the shorter plasma duration experimentally found upon fs laser ablation. Kinetic decay times of several copper (major element) emission lines have been examined together with those relevant to the main plasma parameters. The plasma experimental temperature, derived assuming a Boltzmann distribution, and the electron density following the Saha equation have been compared with the corresponding theoretical data. A satisfactory description of plasma parameters and main matrix constituent composition has been obtained in the time window where local thermal equilibrium was assumed for LIBS data analysis. Improved analytical capabilities are predicted upon delayed detection of plasma emission in femtosecond LIBS, in relation to the better LOD achieved and to the improved data reproducibility expected. Results support the utilization of ultrafast laser sources for trace detection, despite the residual fractionation occurring in the examined range of fluences which affects the linearity of experimental calibration curves built for tin and lead after internal standardization on copper. The validation of model results by experimental data allowed highlighting, from first principles, of the ablation mechanisms for the two temporal regimes and information on how this affects the accurate microanalysis of Cu-based alloys.

Effect of titanium carbide coating on the osseointegration response in vitro and in vivo.

Titanium has limitations in its clinical performance in dental and orthopaedic applications. This study describes a coating process using pulsed laser deposition (PLD) technology to produce surfaces of titanium carbide (TiC) on titanium substrates and evaluates the biological response both in vitro and in vivo. X-ray photoelectron spectroscopy (XPS) analysis revealed the presence of 18.6-21.5% TiC in the surface layer, accompanied by oxides of titanium 78.5-81.4% in the following concentrations: 11.1-13.0% Ti(2)O(3), 50.8-55.8% TiO(2), 14.5-14.7% TiO. Expression of genes central to osteoblast differentiation (alkaline phosphatase, A2 pro-collagen type 1, osteocalcin, BMP-4, TGFbeta and Cbfa-1) were up-regulated in all cell lines (primary human osteoblasts, hFOB1.19 and ROS.MER#14) grown on TiC compared with uncoated titanium when measured by semiquantitative PCR and real time-PCR, whilst genes involved in modulation of osteoclastogenesis and osteoclast activity (IL-6 and M-CSF) were unchanged. Bone density was shown to be greater around TiC-coated implants after 2 and 4 weeks in sheep and both 4 and 8 weeks in rabbits compared to uncoated titanium. Rapid bone deposition was demonstrated after only 2 weeks in the rabbit model when visualized with intravital staining. It is concluded that coating with TiC will, in comparison to uncoated titanium, improve implant hardness, biocompatibility through surface stability and osseointegration through improved bone growth.

Calcium phosphate and fluorinated calcium phosphate coatings on titanium deposited by Nd:YAG laser at a high fluence.

Calcium phosphate coatings are known to enhance long-term fixation, reliability and promote osteointegration of cementless titanium-based implant devices. This study was aimed at the pulsed laser deposition of calcium phosphate coatings onto titanium using hydroxyapatite and hydroxyapatite-fluorapatite targets. The deposition was carried out at the high laser beam fluence conditions, about 12 J/cm(2). The coatings were characterized with respect to their morphology, phase composition and hardness. X-ray energy dispersive analysis revealed the coatings retain their elemental composition, and fluoride content within the film is the same as in the initial target. However, unlike sintered targets, the deposited films contain no apatite-like phases. The hardness of the films, about 18 GPa, is surprisingly high compared to that of hydroxyapatite and hydroxyapatite-fluorapatite ceramic targets. The deposited coatings of 2.7-2.9 microm thickness have uniform and dense microstructure, containing the solidified droplets of the expulsed from the target phase. The uncommon structure and hardness of the films can be attributed to the melting and phase decomposition of the initial material in the laser plasma.