Publications

Composite silk fibroin-poly(3-hydroxybutyric-acid-co-3-hydroxyvaleric-acid) (SF-PHBV) biodegradable coatings were grown by Matrix Assisted Pulsed Laser Evaporation on titanium substrates. Their physicochemical properties and particularly the degradation behavior in simulated body fluid at 37 degrees C were studied as first step of applicability in local controlled release for tissue regeneration applications. SF and PHBV, natural biopolymers with excellent biocompatibility, but different biodegradability and tensile strength properties, were combined in a composite to improve their properties as coatings for biomedical uses. FTIR analyses showed the stoichiometric transfer from targets to coatings by the presence in the spectra of the main absorption maxima characteristic of both polymers. XRD investigations confirmed the FTIR results showing differences in crystallization behavior with respect to the SF and PHBV content. Contact angle values obtained through wettability measurements indicated the MAPLE deposited coatings were highly hydrophilic; surfaces turning hydrophobic with the increase of the PHBV component. Degradation assays proved that higher PHBV contents resulted in enhanced resistance and a slower degradation rate of composite coatings in SBF. Distinct drug-release schemes could be obtained by adjusting the SF:PHBV ratio to controllably tuning the coatings degradation rate, from rapid-release formulas, where SF predominates, to prolonged sustained ones, for larger PHBV content. (C) 2015 Elsevier B.V. All rights reserved.

We report sub-diffraction limited patterning of Si substrate surfaces by laser-initiated liquid-assisted colloidal lithography. The technique involves exposing a two-dimensional lattice of transparent colloidal particles spin coated on the substrate of interest (here Si) immersed in a liquid (e.g. methanol, acetone, carbon tetrachloride, toluene) to a single picosecond pulse of ultraviolet laser radiation. Surface patterns formed using colloidal particles with different radii in the range 195 nm <= R <= 1.5 mu m and liquids with differing indices of refraction (n(liquid)) are demonstrated, the detailed topographies of which are sensitively dependent upon whether the index of refraction of the colloidal particle (n(colloid)) is greater or smaller than n(liquid) (i.e. upon whether the incident light converges or diverges upon interaction with the particle). The spatial intensity modulation formed by diffraction of the single laser pulse by the colloidal particles is imprinted into the Si substrate.

Ba0.95Ce0.05Ti0.9875O3 nanowires were fabricated by sol-gel method using as template a polycarbonate membrane with channels of 100 nm diameter. FE-SEM analyses showed that continuous gel wires of length up to 17 mu m and an average diameter of 81 nm, were obtained. After calcination at 700 degrees C for 1 h, these green 1D nanostructures were converted into well-crystallised wires with an average diameter of 59.7 nm, as high-resolution transmission electron microscopy and selected area electron diffraction indicated. The piezoelectric activity of the Ba0.95Ce0.05Ti0.9875O3 nanowires was investigated using piezoresponse force microscopy (PFM) correlated with atomic force microscopy. The results of PFM measurements indicated that the wires exhibit a significant fraction of ferroelectric domains larger than the grains size and a good piezoelectric response.

Epitaxial (1 - x)Ba(Ti0.8Zr0.2)TiO3 - x(Ba0.7Ca0.3)TiO3, x = 0.45 (BCZT 45), thin films have been deposited on (001) SrTiO3 (STO) and (001/100) SrLaAlO4 (SLAO) substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscopy (HRTEM) confirmed the epitaxial growth of the films. A high structural quality has been evidenced for the BCZT/STO films. Geometric phase analysis (GPA) associated with the HRTEM enabled us to obtain microstrain analysis and the in-plane and out-of-plane lattice parameter variation on different areas. Tetragonality ratio fluctuations at nanoscale level which are relevant for the existence of nanodomains have been evidenced on the BCZT/STO films. The in-plane dielectric constant has been measured on interdigital electrodes deposited by lift-off technique on the top of the films. High values of dielectric permittivity (>3000) combined with low dielectric loss (<0.01) are obtained for BCZT 45 film deposited on STO substrate, showing nearly constant values between 1 kHz and 10 MHz. The high dielectric permittivity of BCZT thin films was attributed to their high structural quality and to the loss of rotation stability of the polarization associated with the presence of nanodomains. This results into a divergence of fluctuations of polarization direction and a peak of dielectric susceptibility. The enhanced switching of such nanodomain configuration was probed by piezoforce microscopy, by writing and reading domains during topography scanning.

Ni-doped (CeO2-delta)-YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure (similar to 18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer-Emmett-Teller, BET; Temperature-Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N-2 sorption measurements highlighted that the mesoporous structure is formed at 600 degrees C and remains stable at 800 degrees C. At 900 degrees C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 degrees C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce3+ + Ce4+) with high percentage of Ce3+ valence state similar to 35 % and (Ni3+ and Ni2+) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.

Hypothesis: The MU [3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium-bromide] cell cytotoxicity indicator is photocatalytically reduced on the surface of TiO2 nanoparticles in phosphate-buffered-saline (PBS) environment. We hypothesize that specific phosphate adsorption may be used to modulate the efficiency of the TiO2 MU reaction through colloidal and semiconductor-liquid interface processes. Experiments: The TiO2 MU reaction kinetics was studied in PBS, with respect to photocatalyst and MIT concentrations and irradiation wavelength. The effects of PBS and electron scavengers (Fe3+ ions) on reaction efficiency and the role of colloidal surface charge in the photocatalytic process were investigated. The structural and spectroscopic characteristics of relevant TiO2-formazan systems were studied by X-ray diffraction, transmission electron microscopy and IR-spectroscopy. Findings: The reaction was pseudo-first order with respect to photocatalyst and showed a negative and fractional partial order with respect to MU. Formazan production rates were directly proportional to radiation wavelength and TiO2 concentration and inversely proportional to the MIT initial concentration. The addition of Fe3+ ions, as well as the absence of PBS, induced strong reaction inhibition. Reaction efficiency and catalyst Zeta potential were enhanced by Na2HPO4 (PBS component) and showed a maximum around the phosphate concentration 0.005 M. Findings: Structural/spectroscopic characterization confirmed the formation of amorphous MU-formazan on the surface of TiO2 and the TiO2-phosphate binding. (C) 2015 Elsevier Inc. All rights reserved.

Interfaces formed by gold and copper on single crystal layers of (0 0 1) PbZr0.2Ti0.8O3 (PZT) produced by pulsed laser deposition and exhibiting outwards polarization are analyzed by X-ray photoelectron spectroscopy. The stoichiometry of the layers reproduces reasonably that of the PZT target. The band bending occurring at the interface between PZT and the metals is investigated by analyzing the core level shifts as function on the metal deposition. It is found that for Au/PZT(0 0 1) the gold layer is not continuous and the observed band bendings can be attributed to a Schottky mechanism, whereas for Cu/PZT(0 0 1) the copper layer is continuous; in this latter case, the observed band bendings towards higher energies (lower binding energies) can be attributed to a concomitant bending due to the Schottky effect together with the disappearance of the initial bending due to the outwards polarization of the samples. Metal Pb is observed to segregate only in the case of Cu/PZT(0 0 1), therefore the surface self-reduction might also be connected to the presence of a metal with lower work function, which for larger coverage forms a continuous metal layer, able to provide electrons to the surface. High resolution transmission electron spectroscopy yielded the disappearance of the tetragonal distortion in the case of Cu/PZT(0 0 1), in line with the assumption of disappearance of the polarization-induced band bending. (C) 2015 Elsevier B.V. All rights reserved.

Ultraviolet laser irradiation of films composed of graphene oxide (GO) and GO-magnetite (Fe3O4) nanoparticles deposited on polydimethylsiloxane substrates is carried out. The irradiations are performed in vacuum and ammonia-rich gas environments. Electron and scanning probe microscopies reveal a rippling process in GO sheets as the accumulation of laser pulses proceeds, being the effect more pronounced with the increase of laser fluence. X-ray photoelectron spectroscopy analyses point to laser-induced chemical reaction pathways in GO completely different depending on the environment and the presence or absence of Fe3O4 nanoparticles. It is demonstrated that GO-based films with diverse type of oxygen- and nitrogen-containing chemical groups can be obtained by means of laser irradiation processes. The sheet resistance of these materials is also correlated to their structure and composition. (C) 2015 Elsevier Ltd. All rights reserved.

The influence of SiO2 layer in a core-shell BNT-BTCe@SiO2 heterostructure on the electrical properties of the BNT-BTCe core ceramic was investigated. The core-shell composite was prepared by coating BNT-BTCe powder with silica layer by a chemical process. BNT-BTCe grain-core was a solid solution of (Bi0.5Na0.5)TiO3 (BNT) and Ba0.95Ce0.05TiO3 (BTCe) with 92: 8 molar ratio. The thickness of the amorphous silica shell was about 128 nm and the size of the grain core was about 250 nm. The structure, microstructure, dielectric, ferroelectric and piezoelectric properties of BNT-BTCe@SiO2 core-shell powder and sintered ceramic were investigated and compared with those of the BNT-BTCe base material. We found that the values of permittivity (epsilon(r)) and dielectric losses of core-shell ceramic are lower and higher, respectively, than those of BNT-BTCe ceramic indicating that the SiO2 does not improve the dielectric properties of BNT-BTCe ceramic. For the BNT-BTCe@SiO2 composite, the silica layer leads to the increase of diffuseness degree of the phase transition and to a better ferroelectric relaxor. The sintered BNT-BTCe@SiO2 heterostructure shows higher remnant polarization P-r, higher coercive field E-c and higher piezoelectric constants (k(t), d(33), g(33), c(33)(E) and S-11(E)) than BNT-BTCe ceramic. The results of our study suggest that BNT-BTCe@SiO2 core-shell material could be interesting for applications in the ferroelectric and piezoelectric domains.

The time-dependent transport through single-molecule magnets (5MM) coupled to magnetic or non-magnetic electrodes is studied in the framework of the generalized Master equation (GME) method. We calculate the transient currents which develop when the molecule is smoothly coupled to the source and drain electrodes. The signature of the electrically induced magnetic switching on these transient currents is investigated. Our simulations show that the magnetic switching of the molecular spin can be read indirectly from the transient currents if one lead is magnetic and it is much faster if the leads have opposite spin polarizations. We identify effects of the transverse anisotropy on the dynamics of molecular states. (C) 2015 Elsevier Ltd. All rights reserved.