National Institute Of Materials Physics - Romania

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.

Six compounds of the types [M(dmbg)(2)]center dot nH(2)O ((1) M: Ni, n = 0; (4) M: Cu, n = 1; Hdmbg: N,N '-dimethylbiguanide) and, respectively, [ML]center dot nH(2)O (where (2) M: Ni, L: L-1, n = 0; (3) M: Ni, L: L-2, n = 0; (5) M: Cu, L: L-1, n = 0 and (6) M: Cu, L: L-2, n = 3, H2L1: ligand resulted from the condensation of (1) with ammonia and formaldehyde and H2L2: ligand resulted from the condensation of (4) with hydrazine and formaldehyde) were characterized as mononuclear species through information provided by NMR, electronic paramagnetic resonance (EPR) and UV-Vis spectroscopy as well as cyclic voltammetry. All data are consistent with macrocyclic formation by condensation. The complexes adopt a distorted square planar geometry resulting from the chelating behaviour of the corresponding ligands. The EPR spectra recorded after the addition of Cu(II) complexes into the corresponding Ni(II) complexes show a well resolved hyperfine structure with the superhyperfine pattern corresponding to four nitrogen atom donors. The cathodically shift of E-pc2 for both series can be correlated with the increased stability of the M(I) species through macrocyclic ligands. Geometry optimization studies for complexes (2), (3), (5) and (6) have further confirmed the experimental data. The pharmacokinetic computational results indicate that the complexes exhibit medium to low intestinal absorption and slow blood-brain barrier permeability but low toxicity. Their predictive pharmacodynamic profiles show that the compounds present the ability to inhibit protease activity. By corroborating the results of the in silico analysis with the experimental ones, the most promising complexes for antimicrobial applications are (1) and (2) and, respectively, (4) and (6) for the development of novel antitumour strategies.

Pottery vessels made of kaolin clay from the Roman Period (2nd, 3rd centuries CE) found in Romula (Re?ca village, Olt County, Romania) from Dacia Inferior (Malvensis) were investigated by petrographic, X-ray diffraction, X-ray fluorescence, thermal analysis, electron microscopy, and mechanical tests. Our results are compared with available data on kaolin clays and pottery vessels from other sites located along the lower course of Danube river and near the Black Sea, namely in Moesia Superior, Moesia Inferior, and Thracia. Archeological and geographical contexts are addressed. Results of our analysis suggest a local production of ceramics in Romula, by using raw materials from the north of Lower Danube, in opposition to the idea that kaolin ware was imported from the provinces south of the Danube.

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.

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.

Photodegradation of the aqueous solutions of acetylsalicylic acid, in the absence (ASA) and the presence of excipients (ASE), is demonstrated by the photoluminescence (PL). A shift of the PL bands from 342 and 338 nm to 358 and 361-397 nm for ASA and ASE in solid state and as aqueous solutions was reported. By exposure of the solution of ASA 0.3 M to UV light, a decrease in the PL band intensity was highlighted. This behavior was revealed for ASA in the presence of phosphate buffer (PB) having the pH equal to 6.4, 7, and 8 or by the interaction with NaOH 0.3 M. A different behavior was reported in the case of ASE. In the presence of PB, an increase in the intensity of the PL band of ASE simultaneously with a change of the ratio between the intensities of the bands at 361-364 and 394-397 nm was highlighted. The differences between PL spectra of ASA and ASE have their origin in the presence of salicylic acid (SAL). The interaction of ASE with NaOH induces a shift of the PL band at 405-407 nm. Arguments for the reaction of ASA with NaOH are shown by Raman scattering and FTIR spectroscopy.

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.

In this paper, we report studies on Al2O3/Ge/Al2O3 trilayer memory structures deposited by magnetron sputtering at room temperature on p-Si substrates coated with 3 nm SiO2. The changes of the structure, morphology and memory properties induced by rapid thermal annealing (RTA) in a broad temperature range 550-900 degrees C have been carefully investigated. High resolution transmission electron microscopy (HRTEM) revealed the existence of distinct RTA effects for different temperature ranges, in correlation with memory properties measured on Al/Al2O3/Ge/Al2O3/SiO2/p-Si/Al devices. Thus, at temperatures smaller than 650 degrees C, Ge diffuses into adjacent Al2O3, the layers remaining amorphous. The memory window increases from as-deposited samples to those annealed at 600 degrees C reaching the maximum of 5.4 V. After RTA at 700 degrees C, Ge nanocrystals (NCs) in intermediate Ge layer and Ge-rich amorphous nanoparticles in Al2O3 tunnel oxide are formed. Increasing RTA temperature to 800 and 900 degrees C, Ge NCs are no longer formed due to Ge strong diffusion. Instead, Ge-rich mixed GeAl oxide NCs of unknown crystalline structure are evidenced by HRTEM. The memory window continuously decreases with annealing temperature in the range 650-900 degrees C. The ON (OFF) charge loss of only 11% (9.8%) was found by extrapolation to 10 years.

We report a novel strategy to enhance the dielectric breakdown strength and the energy storage performance of lead-free relaxor ferroelectric ceramics through the fabrication of semiconductor/relaxor 0-3 type composites based on 0.6Ba(Zr0.2Ti0.8)O-3-0.4(Ba0.7Ca0.3)TiO3 [BZCT] and ZnO. X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM) measurements confirm the formation of semiconductor/relaxor 0-3 type composites, in which ZnO particles are randomly distributed at the grain boundaries of BZCT. Further, the XRD analysis suggests a structural phase change from a tetragonal to a pseudocubic phase as the ZnO content increases from 0 to 5 wt. % in BZCT/ZnO composites. The pseudocubic phase favors the relaxor behavior of the composites as is evident from dielectric studies. The polarization-electric field (P-E) loops reveal the ferroelectric nature of the BZCT/ZnO composites. The energy storage properties of BZCT/ZnO composite ceramics as a function of different wt. % of ZnO are found to be optimum at 1 wt. % with a recoverable energy density of 2.61 J/cm(3) and an efficiency of 74.2%, at an electric field of 282 kV/cm. Besides, an enhancement of 166% in the electric breakdown and 220% in the recoverable energy density was achieved compared to the BZCT ceramics due to the improved density and the large value of Delta P = P-m - P-r (25.55 mu C/cm(2)). Therefore, this work evidences that the formation of the semiconductor/relaxor 0-3 type composites can be an effective way to significantly improve the energy storage performance of lead-free relaxor ferroelectric ceramics. (C) 2020 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.