National Institute Of Materials Physics - Romania

Pure titanium dioxide (TiO2) and graphene oxide (GO) as well as TiO2/GO composite structures were grown by matrix-assisted pulsed laser evaporation (MAPLE) in a controlled oxygen atmosphere. The MAPLE target dispersions were prepared using distilled water as solvent matrix, with TiO2 nanoparticles (NPs) and GO platelets serving as host materials. Two laser sources, a free-running IR Er:YAG (lambda = 2940 nm, tau(fwhm) congruent to 350 mu s, nu = 10 Hz) and a UV KrF* excimer (lambda = 248 nm, tau(fwhm) congruent to 25 mu s, nu = 10 Hz) laser, were used for the transfer and immobilization experiments by infrared (IR)- and ultraviolet (UV)-MAPLE, respectively. The potential physical mechanisms implied in both the IR- and UV-MAPLE processes are discussed, based on numerical simulations of temperature evolution of the distilled water matrix, TiO2 NPs, and GO platelets. Our results demonstrate the effectiveness of IR- and UV-MAPLE processes for the immobilization of nanoentities onto solid substrates. During IR-MAPLE, the laser radiation is primarily absorbed by the water matrix. The materials transferred to the substrate surface resemble the initial starting materials used for the preparation of the MAPLE target dispersions. Conversely, during UV-MAPLE the UV radiation is mainly absorbed by the nanoentities dispersed in the water matrix. The structural transformation of the nanoentities deposited by UV-MAPLE is significant as compared to the starting materials.

A comparative study of two different biocatalytic models, e.g. enzyme immobilized on magnetic particles (EIMP) and cross-linking enzyme aggregates onto magnetic particles (CLEMPA) was performed. The first model was designed as enzyme-immobilized on the magnetic particles surface (EIMP). The second model was constructed as a network structure with the enzyme aggregates and magnetic particles placed into the nodes and polyglutaraldehyde cross-linker as the network ledges. The design was called cross-linking enzyme aggregates onto magnetic particles (CLEMPA). The biocatalysts were prepared using lipase enzyme from Aspergillus niger for catalyzing the glycerol (Gly) conversion to glycerol carbonate (GlyC). The biocatalyst characteristics for both designs (EIMP and CLEMPA) were evaluated using scanning electron microscopy (SEM), laser light scattering (LLS) and UV-Vis techniques. The EIMP model was strongly influenced by the composition of the polymeric layer covering the particles surface, while the size of the magnetic particles affected mostly the CLEMPA design. Also, the biocatalytic capacity of the tested models was evaluated as maximum 52% Gly conversion with 90% GlyC selectivity for EIMP, and 73% Gly conversion with 77% GlyC selectivity for CLEMPA. Both biocatalytic models were successfully used to prepare GlyC from "crude" glycerol collected directly from the biodiesel process (e.g. 49% Gly conversion with 91% GlyC selectivity for EIMP and 70% Gly conversion with 80% GlyC selectivity for CLEMPA).

We investigate the structure of epitaxially grown hexagonal boron nitride (h-BN) on Ir(111) by chemical vapor deposition of borazine. Using photoelectron diffraction spectroscopy, we unambiguously show that a single-domain h-BN monolayer can be synthesized by a cyclic dose of high-purity borazine onto the metal substrate at room temperature followed by annealing at T = 1270 K, this method giving rise to a diffraction pattern with 3-fold symmetry. In contrast, high-temperature borazine deposition (T = 1070 K) results in a h-BN monolayer formed by domains with opposite orientation and characterized by a 6-fold symmetric diffraction pattern. We identify the thermal energy and the binding energy difference between fcc and hcp seeds as key parameters in controlling the alignment of the growing h-BN clusters during the first stage of the growth, and we further propose structural models for the h-BN monolayer on the Ir(111) surface.

Conducting polypyrrole:IrQ(ppy)(2) thin films were obtained by electrochemical method which ensure uniform dispersion of the organometallic in the polymer matrix. A thin layer of about 50 nm polypyrrole: IrQ(pPY)(2) thin films were deposited on the ITO/glass substrate and used for spectroscopic, structural, and electric characterization. The photoluminescence spectrum of polypyrrole:IrQ.(ppy)2 have shown the two main emissions of IrQ(ppy)(2) at 2.44 eV (508 nm) and 2 eV (620 nm) besides of the polypyrrole weak emission centered at 2.55 eV (485 nm). The electric conductivity of the doped polypyrrole thin layer has almost the same conductivity with the undoped polypyrrole thin film suggesting an homogenous polypyrrole:IrQ(ppy)(2) composite which can be used as emissive layer in the OLED's structures. (C) 2014 Elsevier B.V. All rights reserved.

We report results regarding the in vitro toxicology of gamma-Bi2O3 represented by its isomorphous phase Bi12TiO20 (gamma-BTO). The gamma-BTO microparticles were synthesized by two methods: coprecipitation from a bismuth nitrate tetrabutyl titanate solution and solid state reaction of Bi2O3 and TiO2 oxides. The structural and morphological characteristics of the obtained materials were determined using X-ray diffraction (XRD), selected area electron diffraction (SAED), transmission (TEM) and scanning (SEM) electron microscopy. The elemental composition was investigated using energy dispersive spectrometry (EDS). The cytotoxicity and oxidative/nitrosative stress (intracellular reactive oxygen species (ROS) and nitric oxide (NO) release) induced by the studied microparticles in HepG2, SH-SY5Y and 3T3-L1 cell cultures were determined using the MIT, DCF-DA (2 ',7 '-dichlorfluorescein-diacetate) and Griess methods respectively. Depending on the cell type and gamma-BTO concentration, results showed only weak cytotoxic effects after 24 h of gamma-BTO exposure and cell proliferation effects for longer treatment times. Only reduced NO release increases (corresponding to high gamma-BTO concentrations) were detected in case of SH-SY5Y and 3T3-L1 cells. The intracellular ROS production (higher for HepG2 cells) appeared inversely proportional to the gamma-BTO concentration. The obtained results indicated a promising in vitro biocompatibility of gamma-BTO and encourage further studies regarding its potential for biomedical applications. (C) 2014 Elsevier Ltd. All rights reserved.

Dye-doped polymer micro- and nanofibers with tailored light emission properties have great potential for applications in optical, optoelectronic, or photonic devices. In this study, these types of structures were obtained by electrospinning rhodamine 6 G-doped polyvinylpyrrolidone (PVP) using a polymer solution of 10% (mass) concentration in ethanol. Polymer nanofibers with different morphologies (smooth and beaded) and diameters of about 500 nm were obtained using different electrospinning conditions with the same solutions. Fluorescence optical microscopy observations showed that the dye was distributed uniformly in the doped PVP nanofibers. Different shifts were observed when we compared the wavelength of the dye emission band peak of the smooth nanofibers (566 nm) and the wavelength of the dye emission band peak of the beaded fibers (561.5 nm) produced by electrospinning in different conditions with the wavelength of the emission band peak for transparent thin films produced by spin coating (558 nm) using the same polymer solution. This demonstrates that it is possible to tune the optical properties of electrospun dye-doped polymer nanofibers simply by modifying the morphology of the material, i.e., the parameters of the electrospinning process. (C) 2014 Elsevier Ltd. All rights reserved.

In this work we have systematically investigated the evolution of structure and stoichiometry in SrCuO2 films grown on TiO2-terminated SrTiO3 substrates as a function of the substrate temperature. Depending on the growth temperature SrCuO2/SrTiO3 films can exhibit either a pure tetragonal high-pressure phase, or a pure orthorhombic low-pressure phase, or a mixed phase. Our results indicate that at low substrate temperatures the non-equilibrium state of the growth process is responsible for the stabilization of the metastable tetragonal high-pressure structure in SrCuO2 thin films grown on ( 0 01) SrTiO3 substrates, whose lattice matches the metastable structure. In addition, at higher substrate temperatures thermodynamics become dominant over other factors and the SrCuO2 thin films are stabilized in the thermodynamically stable orthorhombic phase. (C) 2014 Elsevier B.V. All rights reserved.

Electropolymerization of diphenylamine (DPA) onto a reduced graphene oxide (RGO) film was carried out to obtain a corresponding RGO/polydiphenylamie (PDPA) composite doped with phosphotungstic acid (H3PW12O40) heteropolyanions (PT). The synthesis was performed in the absence of light, since UVvis spectroscopy and photoluminescence (PL) studies on RGO/DPA blends irradiated by UV light revealed a partial transformation of the DPA monomer into oligomers of PDPA. Raman scattering demonstrates that the electropolymerization of DPA in the presence of H3PW12O40 (PTA) and RGO leads to the formation of PDPA covalently bonded to the RGO sheets (RGO/PDPA:PT). The presence of heteropolyanions in the PDPA matrix (PDPA:PT) is detected by FTIR spectroscopy. Comparing the PL excitation spectra of PDPA:PT and the RGO/PDPA:PT composite highlights an upshift of the band gap that is accompanied by a change in the composition of the PL spectrum in the spectral range of 2.253.54 eV. These changes originate in a charge transfer that takes place at the interface of nongrafted RGO and PDPA:PT. The gradual increase of the PL intensity of RGO covalently grafted with PDPA:PT reveals photochemical reactions under UV irradiation. These involve the CC stretching vibrational mode in the benzene ring of PDPA and indicate the transformation of an RGO/PDPA:PT composite containing HPW12O402 anions into an RGO/PDPA:PT composite stabilized by PW12O403 anions. These results not only provide important insights on the interactions between RGO, conjugated polymers, and stabilizing dopant ions but also impact on the synthesis conditions.

We investigate the equilibrium and nonequilibrium transport through a quantum dot in the Kondo regime, embedded between a normal metal and a topological superconductor supportingMajorana bound states at its end points. We find that the Kondo physics is significantly modified by the presence of theMajorana modes. When the Majorana modes are coupled, aside from the Kondo scale T-K, a new energy scale T* << T-K emerges, that controls the low-energy physics of the system. At lowtemperatures, the ac conductance is suppressed for frequencies below T*, while the noise spectrum acquires a similar to omega(3) dependence. At high temperatures, T >> T-K, the regular logarithmic dependence in the differential conductance is also affected. Under nonequilibrium conditions, and in particular in the {T, B}-> 0 limit, the differential conductance becomes negative. These findings indicate that the changes in transport may serve as clues for detecting the Majorana bound states in such systems. In terms of methods used, we characterize the transport by using a combination of perturbative and renormalization-group approaches.