National Institute Of Materials Physics - Romania

This is the first report on an efficient, "environmentally friendly" chemical reduction method for the synthesis of aminated hyaluronic acid-based silver nanoparticles on the modified surface of titanium dioxide nanoparticles aimed for biological applications. Silver nanoparticles exhibit well-known physical-chemical and optical prop-erties appropriate for different biological applications. Modifying the nanoparticles leads to a change in their expected bioactivity. This represents an important topic for the current research. We have developed a novel aminated hyaluronic acid (HA-EDA)-based protocol to obtain silver nanoparticles, in which HA-EDA was used for the first time as a reducing and stabilizing agent. The effect of the size of silver nanoparticles on the titanium dioxide surface and the chemical composition of the obtained materials were investigated by TEM, XRD, XPS, ATR-FTIR, Raman spectroscopy, NMR and H2-TPR analyses. The antioxidant, in vitro biocompatibility, and antimicrobial activity of the fabricated composites have been evaluated. The results prove that the prepared materials exhibit antimicrobial, antioxidant, and anti-inflammatory activity, thus providing protection against infection and supporting tissue regeneration, these two key effects being of paramount importance for promoting wound healing.

Nanoscale Al-doped yttrium-iron garnets attract enhanced scientific and practical interest in the development of microwave devices due to their remarkable physical-chemical properties, which depend essentially on the method and conditions of synthesis. This work highlights the advantages of a specific two-stage synthesis of Y3AlFe4O12 garnet ferrite nanoparticles by the precipitation in aqueous solutions and deals with the detailed examinations of the precipitates obtained during this process. The results of the complex studies using high resolution transmission microscopy, dynamic light scattering and magnetic measurements have allowed assessing the features of the formation of crystalline structure. It is demonstrated that the sequence of the precipitation of components during the synthesis strongly affects the physical-chemical properties of the formed precipitate (filtration coefficient value, surface charge, micelle's structure) as well as the physical properties of nanoparticles obtained after their heat treatment at 800 degrees C (saturation magnetization, coercive force). Simultaneous precipitation of Fe(OH)3 and Al(OH)3 metal hydroxides, which form one of three crystallographic sub lattices of the garnet structure, at the first stage of the synthesis of ferrite-garnets is revealed to provide higher values of filtration coefficient of the formed precipitate and better technological and physical-chemical parameters of the fabricated garnet nanoparticles that makes this method highly advantageous for industrial application.

The effectiveness of mesoporous SnO2 nickel-decoration as a method for obtaining active electrode materials for bioethanol electrochemical oxidation and the way in which the embedment of a small amount of Black Pearls (BP) affects the electrocatalytic performances of Ni/SnO2 systems were investigated. XPS analysis reveals the presence of NiO, Ni(OH)(2) and Ni2O3 chemical species which favors the oxidation of bioethanol and improves the COx tolerance. Nickel deposition in a reducing environment does not affect the Sn chemistry and the mesoporosity but significantly increases S-BET. A slight amount of BP enhances the S-BET value and a induces a small contribution of larger pores appears. Tafel slopes of 80 mV decade(-1) were estimated for bioethanol oxidation at Ni/SnO2, which favorably compare to those reported in the literature. It was also found that BP incorporation leads to a decrease of the Tafel slope to 70 mV decade(-1), without deleteriously affecting the stability of the electrocatalyst during long-term polarization. EIS results suggested that this improvement might be the combined effect of a lower electrical resistance, a higher specific surface area and a certain contribution from larger pores, which could lead to a better access of the bioethanol species to the electrocatalyst surface.

Hydrothermally formed mesoporous SnO2 was used as a support for nickel chemical deposition and, after subsequent thermal treatment, a high specific surface area (36 m(2) g(-1)) Ni/SnO2 material was obtained. XPS analysis has shown that in the Sn 3d region the spectrum is similar to that of pristine SnO2, whereas Ni species are present on the surface as NiO, Ni2O3 and Ni(OH)(2). Mixing Ni/SnO2 with a small amount of Black Pearls (BP) leads to a significant enhancement of the resulting Ni/SnO2-BP composite activity for nitrite anodic oxidation, presumably due to the higher surface area (115 m(2) g(-1)), to better electrical conductivity and to a certain contribution of the BP to an increase in surface density of the active sites. Ni/SnO2-BP also outperforms pristine BP (in terms of Tafel slopes and electron-transfer rates), most likely due to the fact that the Ni(ii)/Ni(iii) couple can act as an electrocatalyst for nitrite oxidation. A voltammetric method is proposed for the determination of nitrite, over a concentration range of three orders of magnitude (0.05 to 20 mM), with good reproducibility, high stability and excellent sensitivity. The high upper limit of the dynamic range of the analytically useful response might provide a basis for the reliable quantification of nitrite in wastewater.

One of the new materials for next-generation thin film solar cells is Cu2ZnSnSe4 (CZTSe). However, achieving a single-phase CZTSe compound remains a challenge. This study describes the development of Cu2ZnSnSe4 thin films through the sequential deposition of stacked films of non-stoichiometric Cu2SnSe3 (CTSe) and ZnSe by magnetron sputtering. The structural, morphological, and electrical properties as well as the surface chemistry of the films were investigated and compared depending on the growth sequence of the thin films. By using Raman spectroscopy and grazing incidence X-ray diffraction, the tetragonal CZTSe structure was confirmed. Scanning electron microscopy and energy-dispersive spectroscopy measurements of the morphological and compositional properties indicated large grains and dense surfaces with an elemental composition close to the desired stoichiometry in SLG\SnSe2\Cu\ZnSe and SLG\SnSe2\Cu2Se\ZnSe stacks. To ascertain the surface chemistry and unique characteristics of the produced films, additional X-ray photoemission spectroscopy experiments were carried out. The optimal band gap values for the absorber layers were found using conventional spectroscopy, and they ranged from 0.88 to 1.47 eV. According to the electrical measurements, all the films were p-type and have high carrier concentrations between 1016 and 1020 cm-3. Our findings demonstrate that employing a sequential deposition approach and annealing in different atmospheres can yield CZTSe absorber layers with desirable properties, overcoming the challenge of non-stoichiometric CTSe precursors.

In this study, a sol-gel film based on lead sulfide (PbS) quantum dots incorporated into a host network was synthesized as a special nanostructured composite material with potential applications in temperature sensor systems. This work dealt with the optical, structural, and morphological properties of a representative PbS quantum dot (QD)-containing thin film belonging to the Al2O3-SiO2-P2O5 system. The film was prepared using the sol-gel method combined with the spin coating technique, starting from a precursor solution containing a suspension of PbS QDs in toluene with a narrow size distribution and coated on a glass substrate in a multilayer process, followed by annealing of each deposited layer. The size (approximately 10 nm) of the lead sulfide nanocrystallites was validated by XRD and by the quantum confinement effect based on the band gap value and by TEM results. The photoluminescence peak of 1505 nm was very close to that of the precursor PbS QD solution, which demonstrated that the synthesis route of the film preserved the optical emission characteristic of the PbS QDs. The photoluminescence of the lead sulfide QD-containing film in the near infrared domain demonstrates that this material is a promising candidate for future sensing applications in temperature monitoring.

Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N-2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of approximate to 9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.

Core/shell nanocomposites based on magnetic magnetite (Fe3O4) and redox-active cerium dioxide (CeO2) nanoparticles (NPs) are promising in the field of biomedical interests because they can combine the ability of magnetic NPs to heat up in an alternating magnetic field (AMF) with the pronounced antioxidant activity of CeO2 NPs. Thus, this report is devoted to Fe3O4/CeO2 nanocomposites (NCPs) synthesized by precipitation of the computed amount of "CeO2-shell" on the surface of prefabricated Fe3O4 NPs. The X-ray diffraction, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy data validated the formation of Fe3O4/CeO2 "core/shell"-like NCPs, in which ultrafine CeO2 NPs with an average size of approximately 3-3.5 nm neatly surround Fe3O4 NPs. The presence of a CeO2 "shell" significantly increased the stability of Fe3O4/CeO2 NCPs in aqueous suspensions: Fe3O4/CeO2 NCPs with "shell thicknesses" of 5 and 7 nm formed highly stable magnetic fluids with zeta-potential values of >+30 mV. The magnetization values of Fe3O4/CeO2 NCPs decreased with a growing CeO2 "shell" around the magnetic NPs; however, the resulting composites retained the ability to heat efficiently in an AMF. The presence of a CeO2 "shell" generates a possibility to precisely regulate tuning of the maximum heating temperature of magnetic NCPs in the 42-50 degrees C range and stabilize it after a certain time of exposure to an AMF by changing the thickness of the "CeO2-shell". A great improvement was observed in both antioxidant and antiamyloidogenic activities. It was found that inhibition of insulin amyloid formation, expressed in IC50 concentration, using NCPs with a "shell thickness" of 7 nm was approximately 10 times lower compared to that of pure CeO2. For these NCPs, more than 2 times higher superoxide dismutase-like activity was observed. The coupling of both Fe3O4 and CeO2 results in higher bioactivity than either of them individually, probably due to a synergistic catalytic mechanism.

Romula (today Resca, Dobrosloveni Village, Romania) was the largest urban and economic center of Dacia Inferior (Malvensis), a Roman province located in the north of the Lower Danube region. In this context, the city market included workshops for the production of ceramic, metal, stone, bone, and glass objects. In 2013, 2015, and 2018, during excavations of the former Roman city, two rectangular glass furnaces were discovered. One has only one chamber, the other has two chambers. A melted glass layer was found on the walls of furnace no. 1, as well as in one room of furnace no. 2. Broken fragments of glass were also found in both. The furnaces are located in the central area of the Roman city. The evidence suggests that the furnaces belong to secondary glass workshops. The glass may have arrived in raw form, where it was remelted and processed. The discovery of these furnaces contributes to the growing body of evidence for Roman glass production around the empire.1

This study presents conductometric sensors based on Co3O4 nanowires for hydrogen detection at ppb levels. The nanowires are synthesized through thermal oxidation of a 50 nm cobalt layer, exhibiting diameters between 6-50 nm and lengths of 1-5 & mu;m, primarily growing along the (311) direction of spinal Co3O4. Raman investigation reveals five characteristic peaks at 195, 482, 521, 620, and 692 cm(-1), corresponding to symmetric phonon modes of crystalline Co3O4. Electron paramagnetic resonance measurements confirm the presence of a ferromagnetic phase, attributed to incomplete cobalt oxidation, which disappears after 8 h of thermal aging at 400 & DEG;C. Conductometry measurements are performed in the temperature range of 300-500 & DEG;C. At temperatures above 300 & DEG;C, sensors exhibit abnormal n-type semiconducting behavior due to lattice oxygen's involvement in the hydrogen sensing mechanism. Operating at 450 & DEG;C in dry air, the sensor shows a higher 232% response to 100 ppm H-2 compared to ethanol, acetone, methane, carbon monoxide, and nitrogen dioxide. Remarkably, the sensor maintains a consistent conductance baseline even under high humidity (90%) for 25 d, with three-cycle repeatability. This distinctive gas-sensing capability is attributed to the catalytic activity and elevated operating temperature.