National Institute Of Materials Physics - Romania

Mononuclear Mn(II) coordination compound, [Mn(H2L)Cl-2] (1), was synthesized by the reaction of H2L and MnCl2 center dot 4H(2)O in methanol where H2L is tridentate ONO-donor hydrazone ligand [H2L = (E)-N'-(2-hydroxy-5-iodobenzylidene)isonicotinohydrazide]. The reaction of H2L with MnCl2 center dot 4H(2)O in the presence of excess amount of NaN3 in methanol gave an azido bridged dinuclear Mn(III) coordination compound, [Mn-2(L)(mu-N-3)(2)(CH3OH)(2)] (2), whereas in the presence of low amount of NaN3, a phenolate bridged dinuclear Mn(II) coordination compound, [Mn-2(HL)(2)(CH3OH)(2)Cl-2]center dot CH3OH (3), was obtained. These compounds were characterized by elemental analysis, spectroscopic methods, single crystal X-ray analysis and magnetic measurements. The structural studies indicated that the ligand is coordinated as ONO-donor ligand in 1-3 and behave as a neutral, dianionic and monoanionic ligand in compounds 1, 2 and 3, respectively. There is a good agreement between spectroscopic properties and structures of the compounds. Several synthetic attempts indicated that the azide anion has considerable effect on the formation of phenolate bridged dinuclear Mn(II) coordination compound which attributed to its general basic properties. Magnetic measurements indicate the formation of dinuclear molecules with ferromagnetic intramolecular couplings in the case of 2 and 3 as well as with much weaker and distributed antiferromagnetic interactions among the dinuclear units of these compounds. (C) 2020 Elsevier Ltd. All rights reserved.

A new bis-imidazolium salt with two cyanobiphenyl groups and dodecyl sulfate counterion (BIC) was prepared by the metathesis reaction of the bromide salt with sodium dodecyl sulfate. The ILC shows at room-temperature a stable smectic A phase, confirmed by differential scanning calorimetry, polarized optical microscopy, and powder X-ray diffraction investigations. The ILC was doped with TiO2 nanoparticles, having a high specific area, in concentrations of 0.1%, 0.2%, 1% and 2%. Broadband Dielectric Spectroscopy spectra have been registered in the (10-1-107) Hz frequency range, and (250-330) K temperature domain. The study shows that at constant frequency, the conductivity increases with the temperature and dopant concentration. The characteristic times of the observed relaxation processes showed a temperature variation according to the Vogel-Fulcher-Tammann law. Higher values of characteristic times were calculated at the increase of the thickness of the sample. On the other hand, the increase of the concentration of TiO2 nanoparticles leads to a decrease of the characteristic relaxation times. In order to detectwhether the obtained high permittivity increase is due to the Maxwell-Wagner or Electrode Polarization (EP) type phenomena, studies were made on samples of the same concentration, but different thicknesses, and EP was assigned as the main cause of this dielectric constant variation. (C) 2020 Elsevier B.V. All rights reserved.

One of the key elements in assessing traffic safety on the roads is the detection of asphalt conditions. In this paper, we propose an optical sensor based on GeSi nanocrystals embedded in SiO2 matrix that discriminates between different slippery road conditions (wet and icy asphalt and asphalt covered with dirty ice) in respect to dry asphalt. The sensor is fabricated by magnetron sputtering deposition followed by rapid thermal annealing. The photodetector has spectral sensitivity in the 360-1350 nm range and the signal-noise ratio is 10(2)-10(3). The working principle of sensor setup for detection of road conditions is based on the photoresponse (photocurrent) of the sensor under illumination with the light reflected from the asphalt having different reflection coefficients for dry, wet, icy and dirty ice coatings. For this, the asphalt is illuminated sequentially with 980 and 1064 nm laser diodes. A database of these photocurrents is obtained for the different road conditions. We show that the use of both k-nearest neighbor and artificial neural networks classification algorithms enables a more accurate recognition of the class corresponding to a specific road state than in the case of using only one algorithm. This is achieved by comparing the new output sensor data with previously classified data for each algorithm and then by performing an intersection of the algorithms' results.

The influence of Ag and Au nanoparticles and reduced graphene oxide (RGO) sheets on the photodegradation of alpha-lipoic acid (ALA) was determined by UV-VIS spectroscopy. The ALA photodegradation was explained by considering the affinity of thiol groups for the metallic nanoparticles synthesized in the presence of trisodium citrate. The presence of excipients did not induce further changes when ALA interacts with Ag and Au nanoparticles with sizes of 5 and 10 nm by exposure to UV light. Compared to the Raman spectrum of ALA powder, changes in Raman lines' position and relative intensities when ALA has interacted with films obtained from Au nanoparticles with sizes between 5 and 50 nm were significant. These changes were explained by considering the chemical mechanism of surface-enhanced Raman scattering (SERS) spectroscopy. The photodegradation of ALA that had interacted with metallic nanoparticles was inhibited in the presence of RGO sheets.

Almost six decades ago, in Romania a small group of physicists begun to study chalcogenide compositions, motivated primarily by the desire to understand the phase-change phenomenon in these materials, discovered recently, at that time, by Stanford R. Ovshinsky. It took not too long for them to realize the challenges these materials set to the research. With newcomers to the field, the research was broadened. In some cases just for basic research, to model, and to understand the chalcogenide materials, whereas in other cases, the applicative potential was revealed and used. Herein, the evolution of the field of these somewhat exotic materials is followed, listing the main contributions done in Romania, both in basic and applied research.

Core-double shell nylon-ZnO/polypyrrole electrospun nanofibers were fabricated by combining three straightforward methods (electrospinning, sol-gel synthesis and electrodeposition). The hybrid fibrous organic-inorganic nanocomposite was obtained starting from freestanding nylon 6/6 nanofibers obtained through electrospinning. Nylon meshes were functionalized with a very thin, continuous ZnO film by a sol-gel process and thermally treated in order to increase its crystallinity. Further, the ZnO coated networks were used as a working electrode for the electrochemical deposition of a very thin, homogenous polypyrrole layer. X-ray diffraction measurements were employed for characterizing the ZnO structures while spectroscopic techniques such as FTIR and Raman were employed for describing the polypyrrole layer. An elemental analysis was performed through X-ray microanalysis, confirming the expected double shell structure. A detailed micromorphological characterization through FESEM and TEM assays evidenced the deposition of both organic and inorganic layers. Highly transparent, flexible due to the presence of the polymer core and embedding a semiconducting heterojunction, such materials can be easily tailored and integrated in functional platforms with a wide range of applications.

Post-implant infections are a major health problem, and it is well-known that treating them with conventional drugs is accompanied by many disadvantages. The development of new biomaterials with enhanced antimicrobial properties are of major interest for the scientific world. The aim of this study was to synthesize and characterize hydroxyapatite doped with Samarium (Ca10-xSmx(PO4)(6)(OH)(2), x(Sm) = 0.05, 5Sm-HAp) suspensions, pellets and coatings. The 5Sm-HAp coatings on Si substrates were obtained by rf magnetron sputtering technique. The different techniques such as ultrasound measurements, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Glow Discharge Optical Emission Spectroscopy (GDOES), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to examine the obtained coatings. The results showed that the doped Sm ions entered the structure of hydroxyapatite successfully and Sm ions was uniformly doped onto the surface of the support. The depth profile curves of Ca, P, O, H, Ce and Si elements exhibit their presence from a surface to substrate interface as function of sputtering time. XPS analysis indicated as calcium-phosphate structures enriched in Sm3+ ions. Furthermore, the antimicrobial properties of the 5Sm-HAp suspensions, targets and coatings were assessed against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923 and Candida albicans ATCC 10231. The results of the antimicrobial assays highlighted that that the samples presented a strong antimicrobial activity against the tested microbial strains. The results showed that the coatings after 48 h of incubation inhibited the growth of all tested microbial strains under the value of 0.6 Log CFU/mL. This study shows that the 5Sm-HAp samples are good candidates for the development of new antimicrobial agents.

In this work, the metal and semiconducting nanoparticles (AgNPs, ZnONPs and AgZnONPs) were phyto-synthesized using aqueous vegetal extracts from: Caryophyllus aromaticus L. (cloves) and Citrus reticulata L. (mandarin) peels. The morphological, structural, compositional, optical and biological properties (antibacterial activity, and cytotoxicity) of the prepared composites were investigated. The most effective sample proved to be AgZnONPs, derived from cloves, with a minimum inhibitory concentration (MIC) value of 0.11 mg/mL and a minimum bactericidal concentration (MBC) value of 2.68 mg/mL. All the other three composites inhibited bacterial growth at a concentration between 0.25 mg/mL and 0.37 mg/mL, with a bactericidal concentration between 3 mg/mL and 4 mg/mL. The obtained composites presented biocidal activity against Staphylococcus aureus, and biocompatibility (on human fibroblast BJ cells) and did not damage the human red blood cells. Additionally, an important result is that the presence of silver in composite materials improved the bactericidal action of these nanomaterials against the most common nosocomial pathogen, Staphylococcus aureus.

In this work, (Ba0.75Sr0.25) (Ti0.95Co0.05) O-3 perovskite nanostructured material, denoted subsequently as Co-doped BaSrTiO3, was synthesized in a one-step process in hydrothermal conditions. The obtained powder was heat-treated at 800 degrees C and 1000 degrees C, respectively, in order to study nanostructured powder behavior during thermal treatment. The Co-doped BaSrTiO3 powder was pressed into pellets of 5.08 cm (2 inches) then used for thin film deposition onto commercial Al2O3 substrates by RF sputtering method. The microstructural, thermal, and gas sensing properties were investigated. The electrical and thermodynamic characterization allowed the evaluation of thermodynamic stability and the correlation of structural features with the sensing properties revealed under real operating conditions. The sensing behavior with respect to the temperature range between 23 and 400 degrees C, for a fixed CO2 concentration of 3000 ppm, highlighted specific differences between Co-doped BaSrTiO3 treated at 800 degrees C compared to that treated at 1000 degrees C. The influence of the relative humidity level on the CO2 concentrations and the other potential interfering gases was also analyzed. Two possible mechanisms for CO2 interaction were then proposed. The simple and low-cost technology, together with the high sensitivity when operating at room temperature corresponding to low power consumption, suggests that Co-doped BaSrTiO3 has a good potential for use in developing portable CO2 detectors.

Pd deposited on CeOx-MnOx/La-Al2O3 has been prepared as a sensitive material for methane (CH4) detection. The effect of different amounts (1.25%, 2.5% and 5%) of Pd loading has been investigated. The as prepared materials were deposited on Pt microcoils using a drop-coating method, as a way of developing pellistors operated using a Wheatstone bridge configuration. By spanning the operating temperature range between 300 degrees C and 550 degrees C, we established the linearity region as well as the maximum sensitivity towards 4900 ppm of CH4. By making use of the sigmoid dependence of the output voltage signal from the Wheatstone bridge, the gas surface reaction and diffusion phenomena have been decoupled. The pellistor with 5% Pd deposited on CeOx-MnOx/La-Al2O3 exhibited the highest selective-sensitivity in the benefit of CH4 detection against threshold limits of carbon monoxide (CO), sulfur dioxide (SO2) and hydrogen sulfide (H2S). Accordingly, adjusting the percent of Pd makes the preparation strategies of pellistors good candidates towards CH4 detection.