Publications

We report the obtaining of a new composite starting from pyrene thiazole, a compound certified by nuclear magnetic resonance and its covalent grafting on the surface of graphene oxide. Novel material was synthesized in two stages: the first involving transformation of carboxyl groups of graphene oxide into acid chlorides and the second the amide reaction between acid chloride and amine group of pyrene thiazole (PTC). Numerous characterization methods have been used to certify this material, such as: Raman spectroscopy, fluorescence, infrared spectroscopy and X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. Their results show the successful covalent functionalization of graphene oxide with pyrene thiazole through the formation of amide bonds. The electrochemical investigation consisted of evaluating the redox behavior of the carbon screen printed electrodes modified with the new composite (GO-PTC) using caffeic acid, as analyte. From analytical point of view, it is relevant to be able to quantify the presence of caffeic acid and for such reason we used as analytical method the square wave voltammetry. The results showed that the GO-PTC modified carbon screen printed electrodes were able to detect the caffeic acid over more than one order of magnitude (linear working range: 0.005-0.1 mM) and GO-PTC modified electrodes can be considered promising for other analytical investigations.

We present hybrid nanomaterial architectures, consisting of carbon nanowalls (CNW) templates decorated with tungsten oxide nanoparticles, synthesized using a mechanism based on tungsten oxide sublimation, vapor transport, followed by vapor condensation, in the absence or presence of plasma. The key steps in the decoration mechanism are the sublimation of tungsten oxides, when are exposed in vacuum at high temperature (800 degrees C), and their redeposition on colder surfaces (400-600 degrees C). The morphology and chemical composition of the hybrid architectures, as obtained from Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy, are discussed with respect to substrate nature and the physical conditions of synthesis. We pointed out that the decoration process is strongly dependent on the temperature of the CNW templates and plasma presence. Thus, the decoration process performed with plasma was effective for a wider range of template temperatures, in contrast with the decoration process performed without plasma. The results are useful for applications using the sensing and photochemical properties of tungsten oxides, and have also relevance for fusion technology, tungsten walls erosion and material redeposition being widely observed in fusion machines.

The specific roles played by both support and noble metals in light absorption, charge separation, and the formation of center dot OH and O-2(-) (ROS) are analyzed for light-triggered oxidation of phenol (Ph) over pristine and over noble metal (Ag, Au, Pt) -loaded TiO2. Experiments show that the supported noble metals act as a light visible absorber, assist the separation of photo-charges and reduction of O-2 to O-2(-). The O-2(-) oxidizes mildly Ph to oxygenated products (hydroquinone, benzoquinone, and 1,2-dihydroxibenzene). In a parallel process, center dot OH radicals, yielded by TiO2, mineralize Ph to CO2 by fast reaction sequences. Radical quenching and photo electrochemical measurements (surface photovoltage) confirm independently that the production of center dot OH and O-2(-) scale with oxidative conversion of Ph. The selectivity to CO2 and mild oxidation products is the result of the interplay between catalyst activity for center dot OH and for O-2(-) production.

The aim of this paper is to prepare multi-layered ITO thin films by a low cost and environmental-friendly method for different applications (optoelectronics, sensors, etc.). ITO films with 15 layers were obtained by successive depositions using the sol-gel & dip-coating method on three different substrates: glass, SiO2/glass and SiO2/Si. Comparative structural, morphological and optical characterization were performed by X-ray Diffraction (XRD), Atomic Force Microscopy (AFM), Cross Section Transmission Electron Microscopy (XTEM) coupled with Selected Area Electron Diffraction (SAED), Infrared Spectroscopic Ellipsometry (IRSE) and Raman spectroscopy analyses. The optical constants (refractive index n and extinction coefficient k) were determined in a large spectral range (300-27500 cm-1) by spectroscopic ellipsometry (SE). The thicknesses determined by SE were confirmed by HRTEM (High Resolution TEM) measurements which also presents in detail the textural properties of the ITO films at nanometric level. A comparison between IRSE and Raman analysis in the infrared active region was presented.

In this study, the cerium-doped hydroxyapatite (Ca10-xCex(PO4)(6)(OH)(2) with x(Ce) = 0.1, 10Ce-HAp) coatings obtained by the spin coating method were presented for the first time. The stability of the 10Ce-HAp suspension particles used in the preparation of coatings was evaluated by ultrasonic studies, transmission electron microscopy (TEM), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The surface morphology of the 10Ce-HAp coating was studied by SEM and atomic force microscopy (AFM) techniques. The obtained 10Ce-HAp coatings were uniform and without cracks or unevenness. Glow discharge optical emission spectroscopy (GDOES) and X-ray photoelectron spectroscopy (XPS) were used for the investigation of fine chemical depth profiling. The antifungal properties of the HAp and 10Ce-HAp suspensions and coatings were assessed using Candida albicans ATCC 10231 (C. albicans) fungal strain. The quantitative antifungal assays demonstrated that both 10Ce-HAp suspensions and coatings exhibited strong antifungal properties and that they successfully inhibited the development and adherence of C. albicans fungal cells for all the tested time intervals. The scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) visualization of the C. albicans fungal cells adherence to the 10Ce-HAp surface also demonstrated their strong inhibitory effects. In addition, the qualitative assays also suggested that the 10Ce-HAp coatings successfully stopped the biofilm formation.

A dual strategy for the electrochemical detection for 20S proteasome (20S) is proposed, based on the oriented immobilization of a capture monoclonal antibody (Ab beta) on a self-assembled monolayer of 4-mercaptophenylboronic acid (4-MPBA) on gold electrodes, which led to the Au/4-MPBA/Ab beta immunosensor. The methodology comprises the correlation of 20S concentration with (i) its proteolytic activity toward the Z-LLE-AMC substrate, using the Au/4-MPBA/Ab beta/20S, and (ii) the enzymatic activity of an alkaline phosphatase (AlkP) from the AlkP-labeled secondary antibody (Ab(core)-AlkP), which involves the conversion of aminophenylphosphate to the electroactive aminophenol using Au/4-MPBA/Ab beta/20S/Ab(core)-AlkP. The step-by-step construction of the immunosensor and the interactions at its surface were evaluated by surface plasmon resonance and gravimetric analysis with quartz crystal microbalance, showing a high affinity between both antibodies and 20S. Morphological analysis by scanning electron microscopy demonstrated a pattern of parallel lines upon immobilization of Ab beta on 4-MPBA and morphological changes to a well-organized granular structure upon binding of 20S. A voltametric and impedimetric characterization was performed after each step in the immunosensor construction. The two detection strategies were evaluated. It was shown that the immunosensor responds linearly with 20S concentration in the range between 5 and 100 mu g mL(-1), which corresponds to proteasome levels in serum in the case of diverse pathological situations, and LoD values of 1.4 and 0.2 mu g mL(-1) were calculated for the detection strategies. The immunosensor was applied to the detection of 20S in serum samples with recovery values ranging from 101 to 103%.

Properties of epitaxial PbZr0.2Ti0.8O3 (PZT) films deposited on Si substrates were investigated for integration in the present CMOS technology. Polarization is downward oriented, in association with the presence of an internal electric field, and has a lower value compared to the PZT films deposited on single crystal perovskite SrTiO3 (STO) substrates (40 mu C/cm(2) versus 80 mu C/cm(2)), while the dielectric constant is larger (180 versus 120). Large value for the pyroelectric coefficient was also found, 1.22 x 10(-3)C/m(2)K, as for PZT grown on single crystal STO. The macroscopic ferroelectric and pyroelectric properties appear to be affected by the structural quality and stoichiometry of the PZT film. The changes in the electric properties are an effect of the strain gradients induced by the large difference between the thermal expansion coefficients of PZT and Si substrate, leading in turn to Pb oxidation and antisite defect formation compared to PZT films deposited on STO substrates.

Two novel graphene oxide-benzofuran derivatives composites were obtained through the covalent immobilization of [4-hydrazinyl-7nitrobenz-[2,1,3-d]-oxadiazole (NBDH) and respectively, N1-(7-nitrobenzo[c][1,2,5] oxadiazol-4-yl)benzene-1,2-diamine (NBD-PD), on graphene oxide. This covalent functionalization was achieved by activating the carboxylic groups on the surface of graphene oxide by the reaction with thionyl chloride followed by coupling with the amino group of benzofurazane derivatives to obtain the NBD derivatives grafted on graphene oxide. The formation of new materials was check by Raman spectroscopy, fluorescence, infrared spectroscopy and X-ray photoelectron spectroscopy, thermal analysis, scanning electron microscopy, and elemental mapping. The antimicrobial effect of the new composites was evaluated on Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa, both on planktonic and adherent biofilm populations. The cytotoxic effects of the materials on human colon cancer HCT-116 cell line and the normal human fibroblast BJ cell line were evaluated by investigating cell viability and membrane integrity. Apoptosis and colony forming ability of tumor cells were also investigated following exposure to new materials. The biological results of this study have shown that the new materials have potential in combating biofilm formation and also, the tested materials induced cytotoxicity in human colon cancer HCT-116 cell line with limited effects on normal BJ fibroblasts, suggesting their antitumor potential.

Lanthanum orthophosphate (LaPO4) and La0.95-xCe0.05MnxPO4 (x = 0.00, 0.03, 0.10) phosphors were synthesized by a simple and cost-efficient co-precipitation method and the formation of LaPO4 nanorods with a monoclinic P21/n crystal structure was observed. X-ray diffraction pattern analysis indicated a slight distortion of the LaPO4 crystalline structure and an increase of the lattice strain as a consequence of the Mn2+ and Ce3+ dopants incorporation in the host matrix. Scanning electron microscopy revealed that the microstructure of all powders consists of agglomerations of nanorods, which are around 17 +/- 3 nm in diameter and length ranging from 100 nm to 300 nm. Electron paramagnetic resonance measurements have indicated the presence of Mn2+ in isolated species, but also as agglomerates. Ce3+ and Mn2+ doping of LaPO4 resulted also in a decrease of the band gap up to 4.70 eV compared to the un-doped sample. Because of an energy transfer effect from Ce3+ to Mn2+ ions, green emission of Mn2+ ions at around 550 nm was observed upon 275 nm excitation.

Melt spun ribbons of Mn53Al45C2 and Mn52Al46C2 have been synthesized by rapid quenching of the melt with the purpose of monitoring the epsilon-tau phase transformation to show technologically feasible ways to increase magnetic parameters and to illustrate the viability of these alloys as the next generation of rare earth (RE)-free magnets. By differential scanning calorimetry (DSC), activation energies and temperatures of onset of the epsilon-tau phase transformation were obtained. Structural analysis was performed using X-ray diffraction (XRD) and the resulting XRD patterns were quantitatively assessed using full profile Rietveld-type analysis. Appropriate annealing was performed in order to enable the epsilon-tau phase transformation. While hcp epsilon-phase was found to be predominant in the as-cast samples, after appropriate annealing, the tetragonal tau-phase, the one that furnishes the relevant magnetic response, was found to be predominant with an abundance of about 90%. The data suggested a mechanism of hcp epsilon-phase decomposition controlled by the segregation towards the interfacial regions, having the rate of transformation governed by antiphase boundary diffusion processes. Magnetic measurements of annealed sample Mn53Al45C2, consisting of predominant tetragonal tau-phase, showed high values of magnetization and increased coercivity, consistent with an energy product of about 10 MGOe, similar with previously reported magnetization measurements, providing further insight into the realization of future class of RE-free low-cost permanent magnets.