Publications

The electro-oxidation mechanism of free methionine and bound within different peptide sequences was investigated by voltammetry, at glassy carbon electrode, and mass spectrometry. It is proposed that the electro-oxidation of free methionine occurs in two steps, each involving the transfer of one electron and turns pH-independent from mild acid to mild alkaline electrolytes. The first oxidation reaction leads to the formation of a cation radical stabilized either through the amino group resulting in the dehydromethionine intermediate, or by interaction with a neutral methionine molecule leading to production of a dimer cationic radical. The dehydromethionine hydrolysis gave methionine sulfoxide as final oxidation product, whereas a future oxidation of methionine dimer cation radical, i.e. the second electro-oxidation step, results in a methionine dimer dication. Moreover, at high acid media, the protonated amino group influence the electro-oxidation process to take place via proton transfer mechanism. The presence of methionine sulfoxide and of the dimer cationic radical as oxidation products of methionine was confirmed by mass spectroscopy.

Calcium carbonate from marble and seashells is an eco-friendly, sustainable, and largely available bioresource for producing natural bone-like calcium phosphates (CaPs). Based on three main objectives, this research targeted the: (i) adaptation of an indirect synthesis route by modulating the amount of phosphorus used in the chemical reaction, (ii) comprehensive structural, morphological, and surface characterization, and (iii) biocompatibility assessment of the synthesized powdered samples. The morphological characterization was performed on digitally processed scanning electron microscopy (SEM) images. The complementary 3D image augmentation of SEM results also allowed the quantification of roughness parameters. The results revealed that both morphology and roughness were modulated through the induced variation of the synthesis parameters. Structural investigation of the samples was performed by Fourier transform infrared spectroscopy and X-ray diffraction. Depending on the phosphorus amount from the chemical reaction, the structural studies revealed the formation of biphasic CaPs based on hydroxyapatite/brushite or brushite/monetite. The in vitro assessment of the powdered samples demonstrated their capacity to support MC3T3-E1 pre-osteoblast viability and proliferation at comparable levels to the negative cytotoxicity control and the reference material (commercial hydroxyapatite). Therefore, these samples hold great promise for biomedical applications.

Titanium dioxide (TiO2) and TiO2 - graphene oxide (GO) composite layers were deposited by spin coating technique onto SiO2 quartz substrates. TiO2 NPs and GO platelets were used as base materials for the preparation of the starting water/acetone dispersions. Polystyrene (PS) buffer layers were deposited by drop-cast method onto the substrates surface to ensure the adherence of the pure TiO2/PS and TiO2-GO/PS composite layer. The surface morphology and physico-chemical properties of the layers have been determined and correlated with their photocatalytic properties. It was found that GO oxygen functional groups are reduced by the presence of TiO2 NPs in the composite materials. Photodegradation activity under UV-visible light irradiation was studied by measuring the concentration changes in time of organic methylene blue dye in aqueous solutions as well as the chemical oxygen demand for real wastewater samples. The obtained results revealed that the photocatalytic properties of the spin coated composites are determined by the graphene oxide concentration. The effect of the spontaneous reduction of GO in the presence of TiO2 NPs on the photocatalytic activity of the TiO2-GO/PS composites is discussed in detail.

We report the successful growth of multiferroic (Nd,Fe)-doped PbTiO3 thin films with the composition (Pb0.88Nd0.08)(Ti0.93Fe0.05Mn0.02)O-3 (PNFT) using pulsed laser deposition. The deposited films have been investigated by XRD, SEM, energy-dispersive X-ray spectroscopy (EDS), secondary-ion mass spectroscopy (SIMS), atomic force microscopy, magnetic force microscopy, piezoforce microscopy, spectroscopic ellipsometry (SE) and dielectric spectroscopy measurements. PNFT films deposited on different substrates (MgO, SrTiO3 and Nb:SrTiO3) are (001) oriented, preserving the orientation of the single-crystal substrates. EDS mapping and SIMS across the film thickness probed the uniform distribution of all the elements. The refractive index and extinction coefficient have been obtained with the SE software package and refined with an optical-graded model. Magnetic domains and ferroelectric domains have been evidenced at microscopic scale. Good dielectric properties and low loss, comparable to those of bulk materials, have been obtained.

Composite thin coatings of conductive polymer (polyaniline grafted lignin, PANI-LIG) embedded with aminoglycoside Gentamicin sulfate (GS) or magnetite nanoparticles loaded with GS (Fe3O4@GS) were deposited by the matrix-assisted pulsed laser evaporation (MAPLE) technique. The aim was to obtain such nanostructured coatings for titanium-based biomedical surfaces, which would induce multi-functional properties to implantable devices, such as the controlled release of the therapeutically active substance under the action of a magnetic and/or electric field. Thus, the unaltered laser transfer of the initial biomaterials was reported, and the deposited thin coatings exhibited an appropriate nanostructured surface, suitable for bone-related applications. The laser processing of PANI-LIG materials had a meaningful impact on the composites' wettability, since the contact angle values corresponding to the composite laser processed materials decreased in comparison with pristine conductive polymer coatings, indicating more hydrophilic surfaces. The corrosion resistant structures exhibited significant antimicrobial activity against Escherichia coli, Staphylococcus aureus, and Candida albicans strains. In vitro cytotoxicity studies demonstrated that the PANI-LIG-modified titanium substrates can allow growth of bone-like cells. These results encourage further assessment of this type of biomaterial for their application in controlled drug release at implantation sites by external activation.

In the present study we report on the activity, selectivity and stability of the bimodal mesoporous NiO/CeO2-delta-YSZ anodes for IT-SOFCs applications. These materials present high concentration of C3+ ions stably retained in the lattice, which proved to be efficient for the catalytic partial oxidation of CH4 to syngas in the temperature range 600-800 degrees C. The excellent carbon tolerance was proved by a comprehensive XPS analysis, which monitored the amount of carbon before and after catalytic partial oxidation of methane (CPOM) tests. The mesoporous anodes templated by hexadecyltrimethylammonium bromide (CTAB) and tripropylamine (TPA) were obtained using a hydrothermal synthesis route. The effect of Ni and Ce incorporation on the yttria stabilized zirconia (YSZ) structure, texture, morphology and surface chemistry was discussed and correlated with catalytic and electrochemical behavior. The exhaustive characterization of the bulk and surface properties of the catalysts have been accomplished by means of complementary methods: XRD, SEM / EDX / HR TEM, TGA / TPR, XPS. The electrochemical and catalytic performance were improved when the surface contains more reduced ceria and NiO was formed as secondary phase. These features lead to a large number of vacancies and consequently a better oxygen migration, which facilitate the carbon removal.

The work demonstrates growth by the Verneuil method of SrTiO3 single crystals of 30 mm in diameter. Experiments are performed under an industrial environment. Growth was for 4.75 h, i.e., within one production shift. The optimum growth conditions for which the length of the region with bubbles D is zero and the effective length EL (i.e., the crystal length of commercial value) is maximized are for the amount of SrCO3 additive of similar to 3 wt % and for H-2 outer flow rate of similar to 35 L/min. These two parameters show the strongest influence on the bubble-free growth, but other growth parameters (H-2 inner flow rate, O-2 flow rate increase, rotation speed) were also optimized. Selected crystals are characterized from the structural, microstructural, optical, and THz spectroscopy viewpoints, and they are compared with a commercial substrate and with crystals reported in the literature. This work opens the possibility for the industrial growth of large SrTiO3 single crystals and commercialization of large area substrates.

This is the first report on synthesis and photocatalytic activity for trichloroethylene (TCE) degradation under simulated solar light over RbLaTa2O7 layered perovskites with predominant nanowire or platelet morphologies. SEM images witnessed that the one step thermal treatment at 1200 degrees C lead to formation of RbLaTa2O7 nanowires with diameter of 80-320 nm and several microns in length associated in bundles and sharp-edged, merged platelets (minor phase). The two-step annealing at 950 degrees C and 1200 degrees C resulted in decrease of wires bundle population and increase in that of platelets merged in facetted particles. The RbLaTa2O7 nanowires are made of by well-aligned atomic rows with preferred orientation toward the c-axis, relatively free of defect. High density of hydroxyl groups on the sample calcined in mild conditions (RbLaTa_01) favors the photo mineralization of TCE. In contrast, the activity of RbLaTa_02 annealed in harsh conditions (950 and 1200 degrees C), poor in surface hydroxyl groups, remained modest. The weak surface basicity directed the reaction mainly to generation of intermediate chlorinated compounds. Pd and Au were supported on RbLaTa2O7 perovskites as an alternative strategy to boost the removal of chlorinated pollutants by combining photocatalytic (mineralization) and catalytic (hydrodechlorination, HDC) processes. The mineralization of TCE to Cl- was drastically hindered in presence of methanol due to quenching of -OH radicals by alcohol. The results suggested that the density of RbLaTa2O7 surface hydroxyl groups is essential for photo mineralization of TCE whereas the surface carbonate is beneficial for the formation of intermediate chlorinated product.

This research work is dedicated to study structural, morphological, optical and photoluminescence properties of samarium doped calcium sulfate (CaSO4) thin films after exposure to high gamma radiations. Polycrystalline doped CaSO4 thin films have been grown on glass substrates by spray pyrolysis technique and irradiated at different high gamma doses 3, 7, 15 and 40 kGy. Physical characterization of irradiated thin films has been made by X-ray diffraction, Spectrophotometer, Scanning Electron Microscope, Energy Dispersive Spectroscopy, Fluorescence Spectrometer and Thermoluminescence. The most remarkable result, as shown by structural analysis, is the increase of grain size from 52 to a maximum value of 93 nm for 15 kGy gamma dose which indicates a clear enhancement in crystal structure by gamma irradiation. Moreover, the preferred orientation has been immediately changed from (102) plan to (100) just after the first 3 kGy gamma dose. SEM micrographs of irradiated thin layers show deep modifications in surface morphology. Optical transmission spectra have shown a sharp and intense peak at 350 nm wavelength. Band gap energy has been slightly decreased from 3.9 eV before irradiation to 3.6 eV for 40 kGy. A new and strong energy level noted E r , has been emerged and created due to high gamma irradiations in addition to the principal one relative to band gap energy. Other parameters like absorption and extinction coefficients and refractive index have been determined. Thermoluminescence data show a high sensibility to gamma radiations doses which offer opportunities for dosimetry applications. These experimental results suggest the use of irradiated samarium doped calcium sulfate as optical window for space photovoltaic devices where gamma rays are abundant. These results are also helpful for researchers using CaSO4 thin films near nuclear apparatus (nuclear reactors and particle accelerators) or those interested in studying interaction between radiations and condensed matter.

Topological and thermal disorder complicate the mobility characterization in poly(3,4-ethylenedioxythiophene) systems and presently leaves the exact transport mechanisms not fully understood. Here we show that ac-Hall measured by lock-in amplifier is able to resolve the Hall voltage in semimetallic polymers between room temperature and 32 K. These results are evaluated using an organic random phase model. This accounts for the role of tail states and, particularly, for thermal disorder of molecular semiconductors. We report band mobilities up to 3.7 cm(2) V-1 s(-1) in semimetallic polymers occurring in delocalized bands that originate from significant electron coherence across the polymer chains.