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.

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.

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.

Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO4 Olivines.

Transition metal substitution is a key strategy to optimize the functional properties of advanced crystalline materials used as positive electrodes in secondary lithium batteries (LIBs). Here we investigate the structural alterations in the olivine lattice of Mn and Ni substituted LiCoPO4 phase and the impact on performance in LIBs. X-ray diffraction (XRD) and extended X-ray absorption experiments have been carried out in order to highlight the structural alterations induced by partial substitution of cobalt by manganese and nickel. XRD analysis suggests that substitution induces an expansion of the lattices and an increase of the antisite disorder between lithium and transition metal ions in the structure. XAS data highlight negligible electronic disorder but a relevant modulation in the local coordination around the different metal ions. Moreover, galvanostatic tests showed poor reversibility of the redox reaction compared to the pure LCP sample, and this failure is discussed in detail in view of the observed remarkable structural changes.

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).

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.

Structural and Morphological Tuning of LiCoPO4 Materials Synthesized by Solvo-Thermal Methods for Li-Cell Applications.

Olivine-type lithium metal phosphates (LiMPO4) are promising cathode materials for lithium-ion batteries. LiFePO4 (LFP) is commonly used in commercial Li-ion cells but the Fe3+/Fe2+ couple can be usefully substituted with Mn3+/Mn2+, Co3+/Co2+, or Ni3+/Ni2+, in order to obtain higher redox potentials. In this communication we report a systematic analysis of the synthesis condition of LiCoPO4 (LCP) using a solvo-thermal route at low temperature, the latter being a valuable candidate to overcome the theoretical performances of LFP. In fact, LCP shows higher working potential (4.8 V vs. 3.6 V) compared to LFP and similar theoretical capacity (167 mAh·g-1). Our goal is to show the effect of the synthesis condition of the ability of LCP to reversibly cycle lithium in electrochemical cells. LCP samples have been prepared through a solvo-thermal method in aqueous-non aqueous solvent blends. Different Co2+ salts have been used to study the effect of the anion on the crystal growth as well as the effect of solution acidity, temperature and reaction time. Materials properties have been characterized by Fast-Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopies. The correlation between structure/morphology and electrochemical performances has been investigated by galvanostatic charge-discharge cycles.