Publications

Novel biomaterials with promising bone regeneration potential, derived from rich, renewable, and cheap sources, are reported. Thus, thin films were synthesized from marine-derived (i.e., from fish bones and seashells) hydroxyapatite (MdHA) by pulsed laser deposition (PLD) technique. Besides the physical-chemical and mechanical investigations, the deposited thin films were also evaluated in vitro using dedicated cytocompatibility and antimicrobial assays. The morphological examination of MdHA films revealed the fabrication of rough surfaces, which were shown to favor good cell adhesion, and furthermore could foster the in-situ anchorage of implants. The strong hydrophilic behavior of the thin films was evidenced by contact angle (CA) measurements, with values in the range of 15-18 degrees. The inferred bonding strength adherence values were superior (i.e., similar to 49 MPa) to the threshold established by ISO regulation for high-load implant coatings. After immersion in biological fluids, the growth of an apatite-based layer was noted, which indicated the good mineralization capacity of the MdHA films. All PLD films exhibited low cytotoxicity on osteoblast, fibroblast, and epithelial cells. Moreover, a persistent protective effect against bacterial and fungal colonization (i.e., 1- to 3-log reduction of E. coli, E. faecalis, and C. albicans growth) was demonstrated after 48 h of incubation, with respect to the Ti control. The good cytocompatibility and effective antimicrobial activity, along with the reduced fabrication costs from sustainable sources (available in large quantities), should, therefore, recommend the MdHA materials proposed herein as innovative and viable solutions for the development of novel coatings for metallic dental implants.

Using the microwave-assisted sol-gel method, Zn- and Cu-doped TiO2 nanoparticles with an anatase crystalline structure were prepared. Titanium (IV) butoxide was used as a TiO2 precursor, with parental alcohol as a solvent and ammonia water as a catalyst. Based on the TG/DTA results, the powders were thermally treated at 500 degrees C. XRD and XRF revealed the presence of a single-phase anatase and dopants in the thermally treated nanoparticles. The surface of the nanoparticles and the oxidation states of the elements were studied using XPS, which confirmed the presence of Ti, O, Zn, and Cu. The photocatalytic activity of the doped TiO2 nanopowders was tested for the degradation of methyl-orange (MO) dye. The results indicate that Cu doping increases the photoactivity of TiO2 in the visible-light range by narrowing the band-gap energy.

The current study was focused on the potential of pure P25 TiO2 nanoparticles (NPs) and Fe(1%)-N co-doped P25 TiO2 NPs to induce cyto- and genotoxic effects in MRC-5 human pulmonary fibroblasts. The oxidative lesions of P25 NPs were reflected in the amount of 8-hydroxydeoxyguanosine accumulated in DNA and the lysosomal damage produced, but iron-doping partially suppressed these effects. However, neither P25 nor Fe(1%)-N co-doped P25 NPs had such a serious effect of inducing DNA fragmentation or activating apoptosis signaling. Moreover, oxo-guanine glycosylase 1/2, a key enzyme of the base excision repair mechanism, was overexpressed in response to the oxidative DNA deterioration induced by P25 and P25-Fe(1%)-N NPs.

Due to the emergence of antibiotic-resistant pathogens, the need to find new, efficient antimicrobial agents is rapidly increasing. Therefore, in this study, we report the development of new biocomposites based on zinc-doped hydroxyapatite/chitosan enriched with essential oil of Artemisia dracunculus L. with good antimicrobial activity. Techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR) were used in order to evaluate their physico-chemical properties. Our studies revealed that biocomposite materials with nanometric dimension and homogeneous composition could be obtained through an economic and cost-effective synthesis method. The biological assays demonstrated that ZnHA (zinc-doped hydroxyapatite), ZnHACh (zinc-doped hydroxyapatite/chitosan) and ZnHAChT (zinc-doped hydroxyapatite/chitosan enriched with essential oil of Artemisia dracunculus L.) did not exhibit a toxic effect on the cell viability and proliferation of the primary osteoblast culture (hFOB 1.19). Moreover, the cytotoxic assay also highlighted that the cell morphology of the hFOB 1.19 was not altered in the presence of ZnHA, ZnHACh or ZnHAChT. Furthermore, the in vitro antimicrobial studies emphasized that the samples exhibited strong antimicrobial properties against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923 and Candida albicans ATCC 10231 microbial strains. These results are encouraging for the following development of new composite materials with enhanced biological properties that could promote the osteogenic process of bone healing and also exhibit good antimicrobial properties.

Extensive attention and considerable efforts have been made to construct efficient heterogeneous nano -particulate systems for surface chemical reactions to be active in solar light-driven photodegradation. This work addresses current deficiencies of the nanoparticles-focused systems intended for visible light photodegradation by developing a newly-formulated innovative chemically-engineered multi-component system that functions as a recyclabe, nontoxic, active and inexpensive catalyst for photodegradation of tetracyclne antibiotic. Here, we show a straightforward FeOOH nanografting of Al-based SrTiO3 perovskite material as core-shell nanoflower-like heteronanostructure with enhanced solar light-driven photodegradation capability over harmful antibi-otics. A persuasive surface formation mechanism is proposed based on systematic investigation of the assembly process. In-depth caracterization of structural, optical and morphological properties of the prepared samples was investigated using a series of complementary analytical techniques, such as XRD, FE-SEM, HR-TEM, synchrotron XPS, as well as hard and soft XAS in both total electron yield (TEY) and fluorescence yield (TFY). The oxygen -deficient nature of core and shell interface indicates its n-doping and the availability of free charges in core which can be either transferred to the shell or create localized absorption levels into the valence band. This study provides a real opportunity to rationally photocatalysts design with very promising performance in water treatment.

Sodium hexatitanate (Na2Ti6O13) nanoparticles have been synthesized by the hydrothermal method with microwave and conven-tional heating, after which their photocatalytic properties toward an azo dye pollutant degradation have been investigated. Insights into the dynamics and reactivity of the species involved in the photocatalytic mechanism of the (Na2Ti6O13) samples were precisely investigated, for the first time, by X-band electron paramagnetic resonance (EPR) spectroscopy under different experimental conditions. X-ray diffraction structural analysis revealed that all samples crystallized in a monoclinic C2/m structure, with different short-range structural order according to the employed heating, as indicated by Raman. Field-emission scanning electron microscopy and transmission electron microscopy results revealed the formation of rod-and fiber-like nanoparticles with different diameters and lengths. EPR measurements indicated the presence of different Ti3+ point defects and F centers in the samples. X-ray photoelectron spectroscopy analysis proved the presence of oxygen-related defects, but no Ti3+ was detected on the surface. Spin trapping experiments monitored the generation of hydroxyl (OH center dot) radicals over UV-irradiation time. Various parameters contribute to the photocatalytic activity of the samples; however, the type of defect and particle morphology appeared as key factors for enhanced efficiency. Our study provides significant information about paramagnetic defects in Na2Ti6O13 materials and their role in photocatalysis to design other Ti-based photocatalysts.

Nonmagnetic chiral crystals are a new class of systems hosting Kramers-Weyl Fermions, arising from the combination of structural chirality, spin- orbit coupling (SOC), and time-reversal symmetry. These materials exhibit nontrivial Fermi surfaces with SOC-induced Chern gaps over a wide energy range, leading to exotic transport and optical properties. In this study, we investigate the electronic structure and transport properties of CdAs2, a newly reported chiral material. We use synchrotron-based angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT) to determine the Fermiology of the (110)-terminated CdAs2 crystal. Our results, together with complementary magnetotransport measurements, suggest that CdAs2 is a promising candidate for novel topological properties protected by the structural chirality of the system. Our work sheds light on the details of the Fermi surface and topology for this chiral quantum material, providing useful information for engineering novel spintronic and optical devices based on quantized chiral charges, negative longitudinal magnetoresistance, and nontrivial Chern numbers.

The development of new thin-film cathodes triggered a recent research interest in energy storage applications. Over the past years, vanadium oxides have been extensively explored as promising electrodes for batteries owing to their rich valence states and remarkable electrochemical properties. Herein, we report on the synthe-sis of undoped and Sn doped V2O3 thin-films on graphene (G)/Al foil by pulsed laser deposition followed by rapid thermal annealing in N2 at low temperature (similar to 430 degrees C). The obtaining V2O3 phase on graphene/Al foil (G/Al) has been confirmed by X-ray diffraction and Raman and X-ray photoelectron spectroscopy analyses. The synthesized vanadium oxide films were tested as cathodes in coin cells. The electrochemical properties have been systematically investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge discharge (GCD) measurements. A superior electrochemical performance was observed for the V2O3 on G/Al structures, with an initial capacity of around 300 mAh g-1, with respect to the bare G/Al electrode. The use of the Sn-doped (5 mol%) V2O3 thin-films improved slightly the initial capac-ity up to a value of ca. 311 mAh g-1. Both V2O3/G/Al and Sn-doped V2O3/G/Al exhibited excellent cycling performances after 40 cycles with a capacity maintenance at a C-rate C/20 of 317 mAh g-1. Long-term cycling test (up to 200 cycles) showed that the Sn doping could be an excellent strategy to improve the stability of the electrodes, which yielded a capacity loss of only 0.128% per cycle. Possible mechanisms are presented and dis-cussed. This work could serve as point of reference for future developments in the field of batteries employing vanadium oxide-based thin-films deposited by physical vapor deposition techniques.

Background: Based on the current configuration of the International Thermonuclear Experimental Reactor, tungsten (W) was chosen as the armour material. Nevertheless, during operation, the expected power and temperature of plasma can trigger the formation of W dust in the plasma chamber. According to the scenario for a Loss Of Vacuum Accident (LOVA), in the case of confinement failure dust is released, which can lead to occupational or accidental exposure.Methods: For a first evidence of potential risks, fusion devices relevant W dust has been produced on purpose, using a magnetron sputtering gas aggregation source. We aimed to assess the in vitro cytotoxicity of synthesized tungsten nanoparticles (W-NPs) with diameters of 30 and 100 nm, on human BJ fibroblasts. That was systematically investigated using different cytotoxic endpoints (metabolic activity, cellular ATP, AK release and caspase-3/7 activity) and by direct observation with optical and scanning electron microscopy.Results: Increasing concentrations of W-NPs of both sizes induced cell viability decrease, but the effect was significantly higher for large W-NPs, starting from 200 mu g/mL. In direct correlation with the effect on the cell membrane integrity, high concentrations of large W-NPs appear to increase AK release in the first 24 h of treatment. On the other hand, activation of the cellular caspase 3/7 was found significantly increased after 16 h of treatment solely for low concentra-tions of small W-NPs. SEM images revealed an increased tendency of agglomeration of small W -NPs in liquid medium, but no major differences in cells development and morphology were observed after treatment. An apparent internalization of nanoparticles under the cell membrane was also identified.Conclusion: These results provide evidence for different toxicological outputs identified as mechanistic responses of BJ fibroblasts to different sizes of W-NPs, indicating also that small W -NPs (30 nm) display lower cytotoxicity compared to larger ones (100 nm).

In fusion reactors, such as ITER or DEMO, the plasma used to generate nuclear reactions will reach temperatures that are an order of magnitude higher than in the Sun's core. Although the plasma is not supposed to be in contact with the reactor walls, a large amount of heat generated by electromagnetic radiation, electrons and ions being expelled from the plasma will reach the plasma-facing surface of the reactor. Especially for the divertor part, high heat fluxes of up to 20 MW/m(2) are expected even in normal operating conditions. An improvement in the plasma-facing material (which is, in the case of ITER, pure Tungsten, W) is desired at least in terms of both a higher recrystallization temperature and a lower brittle-to-ductile transition temperature. In the present work, we discuss three microengineering routes based on inclusions of nanometric dispersions, which are proposed to improve the W properties, and present the microstructural and thermophysical properties of the resulting W-based composites with such dispersions. The materials' behavior after 6 MeV electron irradiation tests is also presented, and their further development is discussed.