National Institute Of Materials Physics - Romania

In the present study, we developed chitosan/hyaluronan nanoparticles (CS/HY NPs) for tumor targeting with vinblastine sulfate (VBL), that can be directed to the CD44 transmembrane receptor, over-expressed in cancer cells. NPs were prepared by coating with HY-preformed chitosan/tripolyphosphate (CS/TPP) NPs, or by polyelectrolyte complexation of CS with HY. NPs with a mean hydrodynamic radius (R-H) of 110 nm, 12% polydispersity index and negative zeta potential values were obtained by a direct complexation process. Transmission Electron Microscopy (TEM) images showed spherical NPs with a non-homogeneous matrix, probably due to a random localization of CS and HY interacting chains. The intermolecular interactions occurring between CS and HY upon NPs formation were experimentally evidenced by micro-Raman (mu-Raman) spectroscopy, through the analysis of the spectral changes of characteristic vibrational bands of HY during NP formation, in order to reveal the involvement of specific chemical groups in the process. Optimized NP formulation efficiently encapsulated VBL, producing a drug sustained release for 20 h. In vitro studies demonstrated a fast internalization of labeled CS/HY NPs (within 6 h) on K-562 human myeloid leukemia cells. Pre-saturation of CD44 by free HY produced a slowing-down of NP uptake over 24 h, demonstrating the need of CD44 for the internalization of HY-based NPs.

SnO2 nanoparticles have a great potential in photocatalytic and optoelectronic applications by extending their absorbtion and emission from UV to the visible domain. The effect of annealing at 750 degrees C and 1000 degrees C for 3 h in ambient conditions on structural, optical and electrical properties of F&Zn double doped SnO2 nanoparticles synthesized by continuous wave CO2 laser pyrolysis method were investigated for the first time. X-Ray diffraction studies confirmed the expected crystallite size increasing and also the vanishing of divalent tin phases (SnF2, SnO) upon air annealing. Detailed X ray photoelectron spectroscopy (XPS) analysis confirmed that fluorine disappears completely from SnO2 structure at 1000 degrees C. The annealing also induced a reduction in oxygen vacancies as confirmed by Raman spectroscopy and XPS. Transmission FTIR spectroscopy was used for revealing the existence of Sn-O, O-Sn-O, O-H and H-O-H vibrational modes. The optical band gap energies of all annealed samples are in the visible region, decreasing for those that were initially doped with F, and increasing for the only Zn doped sample. Photoluminescence (PL) measurements showed a broad dominant peak in green visible region, around 530 nm. For the sample with the highest content of Zn, PL spectrum shifted to higher wavelengths, respectively to the orange and red regions. The oxygen vacancies concentrations after annealing are correlated with the electrical conductivity of F, F&Zn, and Zn doped SnO2 samples.

Li-ion batteries, widely used in portable electronics, electric vehicles, and energy storage systems, are an integral element of our daily life. However, the limitation of lithium sources, which leads to high prices, prompts the search for alternatives. Recently there has been noticed a rapid interest in Na-ion batteries technology. Especially, suitable cathode structures are investigated to accumulate larger sodium ions. In this paper, the high entropy layered oxide NaMn0.2Fe0.2Co0.2Ni0.2Ti0.2O2 is presented which achieves superior electrochemical properties with a stable capacity of ca. 180 mAh g(-1). The understanding of its high performance is based on a complex study of the multiphase intercalation mechanism. The combination of advanced structural analysis by XAS, in situ XRD, TEM, and computational DFT modelling gives a new concept on the nature of O3-P3 structure reorganization. The presented experimental and theoretical evidence indicates that the P3 phase of layered oxides is energetically favourable for a lower sodium content for specific transition metal-oxide pair distance. Fundamental understanding of the nature of phase transformation is crucial for tailoring structural composition, where the desirable O3-P3 reorganization will occur, resulting in achieving high-performance cathodes.

The synthesis and characterization of novel ionic liquid crystals based on pyridinium salts with Br- and PF6- counterions are described in this work. These pyridinium salts were derived from 4-hydroxypyridine, both by N- and O-alkylation. The 3,4,5-tri(alkyloxy)-benzyl mesogenic unit was attached to the nitrogen atom of the pyridinium ring. Alkyl chains with a different number of carbon atoms (6, 8, 10, 12 and 14) were employed in order to show the effect on the stability of mesophase. The POM (polarizing optical microscopy) and XRD (powder X-ray diffraction) studies indicated that bromide salts with shorter chains C-6, C-8 and C-10 do not show mesomorphic properties, while longer chain analogues with C-12 and C-14 exhibit two enantiotropic columnar phases. Surprisingly, the pyridinium salts with the larger size PF6- counterion do not exhibit liquid crystal properties.

The use of resorbable magnesium alloys in the design of implants represents a new direction in the healthcare domain. Two main research avenues are currently explored for developing or improving metallic biomaterials: (i) increase of their corrosion resistance by designed compositional and structural modifications, and (ii) functionalization of their surfaces by coating with ceramic or polymeric layers. The main objective of this work was to comparatively assess bio-functional coatings (i.e., highly-crystallized hydroxyapatite and silica-rich glass) deposited by radio-frequency magnetron sputtering (RF-MS) on a biodegradable Mg-0.8Ca alloy (0.8 wt.% of Ca). After probing their morphology (by scanning electron microscopy) and structure (by Fourier transform infrared spectroscopy and grazing incidence X-ray diffraction), the corrosion resistance of the RF-MS coated Mg-0.8Ca substrates was electrochemically tested (in synthetic biological media with different degrees of biomimicry), and their cytocompatibility was assessed in osteoblast and fibroblast cell cultures. By collective assessment, the most promising performances, in terms of mass loss (similar to 7% after 12 days), hydrogen release rate (similar to 6 mL/cm(2) after 12 days), electrochemical corrosion parameters and cytocompatibility, were obtained for the crystalline HA coating.

TiO2-based mixed oxide-carbon composite supports have been suggested to provide enhanced stability for platinum (Pt) electrocatalysts in polymer electrolyte membrane (PEM) fuel cells. The addition of molybdenum (Mo) to the mixed oxide is known to increase the CO tolerance of the electrocatalyst. In this work Pt catalysts, supported on Ti1-xMoxO2-C composites with a 25/75 oxide/carbon mass ratio and prepared from different carbon materials (C: Vulcan XC-72, unmodified and functionalized Black Pearls 2000), were compared in the hydrogen oxidation reaction (HOR) and in the oxygen reduction reaction (ORR) with a commercial Pt/C reference catalyst in order to assess the influence of the support on the electrocatalytic behavior. Our aim was to perform electrochemical studies in preparation for fuel cell tests. The ORR kinetic parameters from the Koutecky-Levich plot suggested a four-electron transfer per oxygen molecule, resulting in H2O. The similarity between the Tafel slopes suggested the same reaction mechanism for electrocatalysts supported by these composites. The HOR activity of the composite-supported electrocatalysts was independent of the type of carbonaceous material. A noticeable difference in the stability of the catalysts appeared only after 5000 polarization cycles; the Black Pearl-containing sample showed the highest stability.

In recent years, iron oxides-based nanostructured composite materials are of particular interest for the preparation of multifunctional thin films and membranes to be used in sustainable magnetic field adsorption and photocatalysis processes, intelligent coatings, and packing or bio-medical applications. In this paper, superparamagnetic iron oxide (core)-silica (shell) nanoparticles suitable for thin films and membrane functionalization were obtained by co-precipitation and ultrasonic-assisted sol-gel methods. The comparative/combined effect of the magnetic core co-precipitation temperature (80 and 95 degrees C) and ZnO-doping of the silica shell on the photocatalytic and nano-sorption properties of the resulted composite nanoparticles were investigated by ultraviolet-visible (UV-VIS) spectroscopy monitoring the discoloration of methylene blue (MB) solution under ultraviolet (UV) irradiation and darkness, respectively. The morphology, structure, textural, and magnetic parameters of the investigated powders were evidenced by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) measurements, and saturation magnetization (vibrating sample magnetometry, VSM). The intraparticle diffusion model controlled the MB adsorption. The pseudo- and second-order kinetics described the MB photodegradation. When using SiO2-shell functionalized nanoparticles, the adsorption and photodegradation constant rates are three-four times higher than for using starting core iron oxide nanoparticles. The obtained magnetic nanoparticles (MNPs) were tested for films deposition.

NiO-sensitive materials have been synthesized via the hydrothermal synthesis route and calcined in air at 400 degrees C and, alternatively, at 500 degrees C. Structural, morphological, and spectroscopic investigations were involved. As such, the XRD patterns showed a higher crystallinity degree for the NiO calcined at 500 degrees C. Such an aspect is in line with the XPS data indicating a lower surface hydroxylation relative to NiO calcined at 400 degrees C. An HRTEM microstructural investigation revealed that the two samples differ essentially at the morphological level, having different sizes of the crystalline nanoparticles, different density of the surface defects, and preferential faceting according to the main crystallographic planes. In order to identify their specific gas-sensing mechanism towards CO exposure under the in-field atmosphere, the simultaneous evaluation of the electrical resistance and contact potential difference was carried out. The results allowed the decoupling of the water physisorption from the chemisorption of the ambient oxygen species. Thus, the specific CO interaction mechanism induced by the calcination temperature of NiO has been highlighted.

In this study curcumin was immobilized in a silica matrix to overcome its poor aqueous solubility and rapid degradation profile. Two kinds of sol-gel powders based on colloidal silica were synthesized and characterized, one prepared with an ethanolic solution of curcumin and the other using cethyltrimethylammonium bromide (CTAB) to solubilize the dye. The successful integration of curcumin in the matrix as well as the interaction with the components of the composite powders was validated by different analysis methods (DSC, FTIR). The samples morphology was evaluated by SEM. UV-Vis and fluorescence studies showed that curcumin was stable, in its enol configuration in both matrices. The sensitivity to ammonia was proved by exposing the powders to NH3 vapors in a sealed vessel. Color changes were measured with a colorimeter. UV-Vis spectra showed that the enol form of the dye in EtOH/CTAB based SiO2 matrices was energetically stable under NH3 atmosphere, even after being kept a few days at low temperature. A fluorescence quenching of both samples was noticed due to interaction curcumin-ammonia. Both samples have antimicrobial properties, the CTAB containing one being more efficient. The EtOH/CTAB based SiO2 powders may represent a novel signaling and antimicrobial system, useful for food or pharmaceutical applications. [GRAPHICS] .

For high-field power applications of high-temperature superconductors, it became obvious in recent years that nano-engineered artificial pinning centers are needed for increasing the critical current and pinning potential. As opposed to the artificial pinning centers obtained by irradiation with various particles, which is a quite expensive approach, we have studied superconducting samples having self-assembled defects, created during the sample fabrication, that act as effective pinning centers. We introduced a simple, straight-forward method of estimating the frequency-dependent critical current density by using frequency-dependent AC susceptibility measurements, in fixed temperatures and DC magnetic fields, from the positions of the maxima in the dependence of the out-of-phase susceptibility on the amplitude of AC excitation magnetic field. The results are compatible with a model that stipulates a logarithmic dependence of the pinning potential on the probing current. A mathematical derivation allowed us to estimate from the experimental data the pinning potentials in various samples, and in various DC magnetic fields. The resulted values indicate large pinning potentials, leading to very small probability of magnetic flux escaping the pinning wells, hence, leading to very high critical currents in high magnetic fields.