Publications

Four new Ni(II) complexes with acrylate and imidazole (Him) or imidazole derivatives [2-methylimidazole(2-MeIm)/5-methylimidazole(5-MeIm)/2-ethylimidazole(2-EtIm)] as ligands were prepared and characterized. All coordination compounds were characterized by elemental analysis, infrared (FTIR) and ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, mass spectroscopy, magnetic moments measurements and thermal analysis (TG). The resulted complexes were formulated as follows: [Ni(HIm)(2)(acr)(2)] (1), [Ni(2-MeIm)(2)(acr)(2)(H2O)] center dot H2O (2), [Ni(5-MeIm)(2)(acr)(2)]center dot H2O. (3), [Ni(2-EtIm)(2)(acr)(2)(H2O)] center dot H2O (4). On the basis of magnetic moments measurements and on UV-Vis-NIR spectra, for all Ni(II) complexes was proposed an octahedral stereochemistry. Acrylate ions act as bidentate in complexes (1) and (3); meanwhile, in (2) and (4) they behave as bidentate and unidentate. Antimicrobial activity of complexes was investigated on ATCC reference and clinical microbial strains. The MIC (minimum inhibitory concentration) values revealed moderate antimicrobial activity of complex (1) against Enterococcus faecium and of complex (2) against Pseudomonas aeruginosa and Bacillus subtilis.

Sm3+, Pr3+ and Dy3+-doped Ca3Nb1.6875Ga3.1875O12 - CNGG and Ca3Li0.275Nb1.775Ga2.95O12 - CLNGG crystals are of interest as solid-state laser materials emitting in the yellow-orange spectral range, especially for diode pumping due to their partially disordered nature. In this work, for the first time to our knowledge, single crystals of Sm, Pr and Dy-doped CNGG and CLNGG crystals were grown by the Czochralski method. For the doping of CNGG and CLNGG crystals, five new stoichiometric garnets were synthesised by solid-state reaction method: praseodymium-gallium-garnet (PrGG), dysprosium-gallium-garnet (DyGG) and praseodymium-lithium-niobium gallium-garnet (PrLNGG), samarium-lithium-niobium-gallium-garnet (SmLNGG), and dysprosium-lithium-niobium-gallium-garnet (DyLNGG). Samarium-gallium-garnet (SmGG) was also sintered and used for the doping of Sm:CNGG crystal. Structural properties of sintered materials and grown crystals were investigated by X-ray diffraction and the chemical compositions of the grown crystals were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) method. The spectroscopic investigations of the grown crystals have shown that they are promising laser materials in the yellow-orange spectral range.

Interfacial properties of organic adsorbates featuring aromatic -orbitals on metal surfaces play an important role for organic electronics and spintronics. Pyrene is a flat aromatic molecule with a size between ultimately small benzene and extended graphene segments. The deposition of pyrene molecules onto clean and reactive surfaces with a sub-monolayer coverage under ultra-high vacuum (UHV) conditions is challenging, since pyrene is a solid with a high vapor pressure. Here, a sublimation procedure under UHV and image pyrene adlayers on in situ prepared Au(111) and Fe/W(110) substrates by means of low-temperature scanning tunneling microscopy is presented. For Au(111), the molecule-surface interaction is weak as indicated by the specific herringbone reconstruction of the Au(111) surface that is visible through the self-assembled pyrene adlayer. Pyrene desorption due to weak intermolecular interaction self-limits the growth to one monolayer (ML). On the more reactive 2-4 ML thick Fe films on W(110), the molecular order of the pyrene adlayer sensitively depends on the Fe thickness-dependent dislocation pattern at the substrate surface. Irregular arrangements occur for 1 ML Fe and near substrate dislocations for 2-4 ML Fe. Self-assembled ordered arrays form predominantly for 2 ML Fe, where the dislocation pattern leaves sufficiently large unperturbed areas between the dislocation lines.

One of the most promising ways for the realization of multi-functional materials is the integration of oxides with different properties in artificial heterostructures. In this paper, a novel piezoelectric-ferromagnetic heterostructure consisting of 0.92Na(0.5)Bi(0.5)TiO(3)-0.08BaTiO(3) (abbreviated as BNT-BT0.08) and CoFe2O4 layers is fabricated on Si-Pt substrate, by sol-gel method coupled with spin-coating technique. The composite thin film shows only perovskite Bi0.5Na0.5TiO3-like rhombohedral phase and CoFe2O4 cubic phase. The thickness of CoFe2O4 and BNT-BT0.08 layers is similar to 280 and similar to 400 nm, respectively. BNT-BT0.08/CoFe2O4 heterostructure thin film shows a saturation magnetization of 0.11 emu/g at 5 K and 0.07 emu/g at 295 K, dielectric constant of 235 at 1 kHz and tunability of 70% at 1 kHz and an electric field E = 110 kV/cm. The results reveal that the investigated hybrid piezoelectric/ferromagnetic structure shows piezoelectric behavior, good ferroelectric and ferromagnetic properties. This bilayer composite can be used in miniature low-frequency magnetic sensor and piezoelectric sensor for biomedical domain.

Refined structure of the ferritic phase induced by mechanical milling (under reducing atmosphere) and its thermal stability are required in various applications of nanostructured ferritic alloys. The impurification with nitrogen and oxygen uptaken from the air is very probable during ball-milling, especially at the long-time high-energy milling conditions. As a rule, these interstitial impurities in as-milled powders are in quantities under the sensibility limit of conventional measurement techniques, such as XRD and SEM/ EDS. To evidence the tendency for microstructure modification by impurities introduced during milling, the Fe-14Cr-3W-0.4Ti-0.25Y(2)O(3) (Fe14Cr) ferritic steel powders (re)loaded in air and milled up to 170 h with interruption of the milling process, and heated up to 1373 K were investigated by thermal analysis in correlation with X-ray diffraction and scanning electron microscopy. XRD failed to detect the impurities in powders milled up to 38 h in air although a consistent mass loss related to the degassing of N-2 was registered in thermogravimetric, TG, curves. (Fe,Cr)(4)N, fcc-c, (Fe, Cr)(2)O-3 impurity phases in powders milled over 38 h in air and (Fe,Cr)(2)O-4 formed upon heating were readily detected by XRD. The analysis of these results allowed to better understand the impurification process and to generalise it for any as-milled Fe-Cr-based alloy powder processed in any milling conditions irrespective of the milling atmosphere, duration and thus, of amounts of contaminants. The quality of three powders milled for 170 h in three different conditions was compared: in air, under an argon atmosphere with interruptions of the milling process and under an argon atmosphere without interruption of the milling process. The contamination of powder milled for 170 h under an argon atmosphere without interruption of the milling process is insignificant (corresponding to less than 0.5 mass% mass loss in TG) as compared to powders obtained in the other two milling conditions. New approaches for minimising the contamination from air are suggested.

Arrays of Ni submicron wires surrounded by poly (vinylidene fluoride) (PVDF) submicron tubes were prepared via solution-processed polymer and Ni electrodeposition into anodic aluminum oxide template. The PVDF solution was filtered in vacuum through the template and the resulting dried structure was used for the electrodeposition of Ni wires. The obtained core-shell submicron wire structure consists of a metallic magnetic nanowire core of about 50 mu m in length and about 300 nm diameter surrounded by a polymer tube shell with thickness less than 10 nm. The specific ferroelectric beta-phase of the polymer was obtained whereas the magnetic behavior of the Ni-cores was proven to be specific to an array of ferromagnetic Ni cylindrical wires (about 0.62 mu(B)/Ni atom) with magnetization reversal mechanisms dominated by dipolar interactions and domain wall displacements. No significant differences of the magnetization reversal mechanism were observed in case of Ni submicron wires surrounded by PVDF tubes and similar Ni wires without PVDF shell, suggesting that magneto-coupling effects in such systems might be observed only by measuring the perturbation of the electric state of the polymer shell under a magnetic excitation of the Ni cores.

Pd nanoparticles are stabilized onto the surface of Fe3O4-entrapped poly(aminoethyl acrylamide) via functionalization of polymer with a new class of NNN-pincer ligand providing a high loading and stable catalyst for aerobic oxidation of alcohols to aldehydes. Varieties of alcohols are oxidized to the corresponding aldehydes with good selectivity using 0.95 mol% Pd catalyst. The catalyst is reusable (5 runs) without loss of activity and leaching or agglomeration of Pd nanoparticles while structural regularity of the catalyst is preserved. Oxidation of benzyl alcohol is also scaled up to a few grams. (C) 2018 Elsevier B.V. All rights reserved.

A series of liquid crystals with various lanthanide ions (Eu-III, Sm-III, and Tb-III) was designed and prepared starting from the corresponding lanthanide nitrates and N-alkylated 4-pyridone derivatives bearing mesogenic 3,4,5-tris(alkyloxy)-benzyl moieties (alkyl=hexyl, octyl, decyl, dodecyl, tetradecyl, or hexadecyl). These new lanthanidomesogens were investigated for their mesogenic properties by a combination of differential scanning calorimetry, polarizing optical microscopy, and temperature-dependent powder X-ray diffraction (XRD). Their thermal stability was assessed by thermogravimetric analysis. All of these complexes show enantiotropic liquid-crystalline behavior with lamellar (SmA) phases in the case of shorter-chain complexes (C-6 and C-8) or hexagonal columnar phases (Col(h)) for complexes with longer alkyl chains (C-12, C-14, and C-16), which were assigned on the basis of their characteristic textures and XRD studies. For complexes with an intermediate number of carbon atoms in the side chains (C-10), both a lamellar phase at lower temperatures and a Col(h) phase at higher temperatures were evidenced. In the solid state, all these complexes show characteristic emissions assigned to the corresponding lanthanide ion. In addition, the luminescence decay curves showed single-exponential decays with characteristic times in the millisecond range (0.75-0.90 ms for Eu-III, 0.045-0.060 ms for Sm-III, and 0.75-1.05 ms for Tb-III).

We investigate the effect of the nature of the substrate and the bottom interface on the out-of-plane polarization orientation of ultrathin (10-nm) lead zirconate titanate (PZT) thin films of (001) orientation by photoelectron spectroscopy of samples without surface contamination. The substrate nature is varied between insulator (strontium titanate, STO) and semiconductor (Nb-doped STO, STON) and finally to a metal with a work function lower than that of PZT (strontium ruthenate, SRO). Outward polarization is obtained for PZT/STON(001) and inward polarization is obtained for PZT/STO(001) and PZT/SRO(001). Explanations are given for all these typical cases, the main elements being charge accumulation for compensation of the depolarization field, self-doping of PZT films, and the interface electric field driving the orientation of the polarization of the ferroelectric films. We find p-type self-doping is correlated with the inward polarization, and the driving field is formed between a negatively charged region with negatively ionized acceptors near the interface with the substrate and the p-type degenerate region with holes accumulated inside, toward the surface. This mechanism may be reversed under the assumption of n-type self-doping, positively ionized donors near the interface, and accumulated electrons toward the surface in the case of an interface with a substrate with a higher work function, being in line with recent data (PZT/Pt or BaTiO3/SRO).

A versatile method based on the matrix assisted pulsed laser evaporation (MAPLE) technique was used for the fabrication of graphene-based electrodes for application in supercapacitors. The simultaneous deposition and chemical transformation of graphene oxide (GO) and GO-NiO nanoparticles was attained by including nitrogen-containing chemically reactive compounds (ammonia, urea and melamine) in aqueous MAPLE targets. Morphological analyses reveal the formation of hundreds of nanometres to tens of micrometres thick porous films on both plastic and metallic flexible substrates. Structural and compositional studies, carried out by transmission electron microscopy, and Raman and X-ray photoelectron spectroscopies, disclose significant deoxidation and nitrogen doping of the GO material. The electrodes reveal remarkable electrochemical performance, showing a maximum volumetric capacitance of 350 F cm(-3) (9 mF cm(-2) areal capacitance) in aqueous electrolyte. Symmetric supercapacitors fabricated with these electrodes reveal excellent long-term stability at high specific intensities. From the obtained results, it can be asserted that the reactive inverse MAPLE method stands out as a promising technology not only for the adaptable fabrication of flexible graphene-based composite electrodes but also for a wide variety of advanced functional materials for diverse applications.