Publications

The paper describes an innovative bio-design of some hybrid nanoarchitectures containing bioartificial membranes and silver nanoparticles phytogenerated by using a natural extract Caryophyllus aromaticus (cloves) that contains many bioactive compounds. Two kinds of liposomes with and without chlorophyll a (Chla) obtained through thin film hydration method were used to achieve bio-green-generated hybrids by a simple, cost effective bottom-up approach. The characteristic peaks of CE-nAg monitored by UV-Vis absorption have firstly demonstrated the biohybrids formation. The slightly blue shift and fluorescence quenching observed by fluorescence emission spectra highlighted the formation of hybrid systems by biointeraction between lipid vesicles and silver nanoparticles. The incorporation of silver nanoparticles in lipid vesicles resulted in significant changes of FT-IR spectra of liposomes, indicating a reorganization of biomimetic membranes. All the microscopic methods (SEM, AFM and TEM) confirmed the biosynthesis of "green" AgNPs together with associated biohybrids, their spherical and quasi-spherical shapes with nano-scaled size. By TEM assay it was shown that CE-nAg are surrounded by petal like cloud structures that consist of biopolymers like proteins or polysaccharides and other phytochemicals arising from clove extract. EDS spectra confirmed the formation of phyto-nanoAg and also the presence of silver in the biohybrids. In addition, Selected Area Electron Diffraction showed characteristic polycrystalline ring patterns for a cubic structure of the clove-generated AgNPs. The hybrid materials showed efficient physical stability, ie. xi value of - 28.0 mV (for biohybrids without Chla, BH) and of - 31.7 mV (for biohybrids labelled with Chla, Chla-BH), assured by strong electrostatic repulsive forces between particles. The "green" nano-silver particles (CE-nAg) showed remarkable antioxidant activity (AA = 90.2%). The biohybrids loaded with clove-AgNPs proved to be more effective, scavenging about 98.8% of free radicals (in case of ChlaBH), and of 92.6% (in case of BH). The antibacterial effectiveness showed that green AgNPs combine in a synergistic manner the antibacterial properties of clove extract with those of silver, resulting in an enhancement of inhibition diameter, by 20%. Chla-BH proved to be more potent against Escherichia coli, than BH, exhibiting an inhibition diameter of 42 mm. Regarding the in vitro cytotoxicity against tumour cells, the CE-nAg concentration significantly influenced the cell viability, ie. IC50 was 3.6% (v/v) for HT-29 cells. Chla-BH was more effective against HT-29 cancer cells at the concentrations ranging from 0 to 18% (v/v), when the normal cells were not affected. Clove-generated AgNPs exhibited haemolytic activity against hRBCs, while the biohybrids were haemocompatible. The action mechanism on the two cell lines (mouse fibroblast L929 cells and human colorectal adenocarcinoma HT-29 cells) investigated by fluorescence microscopy demonstrated that CE-nAg killed almost all the cells (94%) through necrosis at a concentration of 33.4% (v/v). The treatment of HT-29 cells with BH resulted in: 71.5% viable cells, 19.5% apoptotic and only 9% necrotic cells, while in the case of Chla-BH treatment, only 77.5% cells were viable, 16% cells were apoptotic and 6.5% were necrotic. In this way, the developed silver-based nanoparticles can represent viable promoters to develop new biohybrids with improved features, e.g. antioxidant and antibacterial effectiveness, haemolytic activity and greater specificity towards tumour cells.

Ferroelectric capacitors based on aluminium (Al) doped hafnium oxide (HfO2) thin films grown on silicon substrates were fabricated by Atomic Layer Deposition (ALD), taking into account two methods. The first one involved the growth of a binary oxide, in a laminar way, by alternating the ALD cycles of HfO2 and Al2O3, and the second, the two precursors were sequentially mixed on the surface. The composition and structure of deposited aluminium doped hafnium oxide (Al: HfO2) thin films have been studied using X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray diffraction (GIXRD). XPS measurements show the formation of opposite ferroelectric polarization areas. Via GIXRD, it was found that the Al: HfO2 films deposited on Si have a structure with polycrystalline domains. Recording and investigation of ferroelectric domains were performed by Piezoresponse Force Microscopy (PFM), while the electrical performances of obtained devices were analysed by capacitance-voltage (C-V) and current-voltage (I-V) characteristics. The PFM measurements show there is a mechanical non-zero response even outside the written area and for an appropriate value of the electrical stress the difference in phase between successive areas is saturated to a value close to 180 degrees. The atomic force microscopy (AFM) analyses indicate a very low value of roughness average, for all grown thin films, similar to 0.2 nm, for a thickness of similar to 7 nm. From C-V characteristics, the memory window was extracted and the calculated values were found to be 0.8 V for the device obtained by the first ALD method, and 0.44 V for the second one, respectively. Moreover, in the case of the device based on the ferroelectric layer grown by the second ALD method, the memory window extends over a much wider applied voltage domain, in the range (+/- 4 V; +/- 8 V), at a signal of 100 kHz.

In this work, rapid thermal annealing (RTA) was applied to indium tin oxide (ITO) films in ambient atmosphere, resulting in significant improvements of the quality of the ITO films that are commonly used as conductive transparent electrodes for photovoltaic structures. Starting from a single sintered target (purity 99.95%), ITO thin films of predefined thickness (230 nm, 300 nm and 370 nm) were deposited at room temperature by radio-frequency magnetron sputtering (rfMS). After deposition, the films were subjected to a RTA process at 575 degrees C (heating rate 20 degrees C/s), maintained at this temperature for 10 minutes, then cooled down to room temperature at a rate of 20 degrees C/s. The film structure was modified by changing the deposition thickness or the RTA process. X-ray diffraction investigations revealed a cubic nanocrystalline structure for the as-deposited ITO films. After RTA, polycrystalline compounds with a textured (222) plane were observed. X-ray photon spectroscopy was used to confirm the beneficial effect of the RTA treatment on the ITO chemical composition. Using a Tauc plot, values of the optical band gap ranging from 3.17 to 3.67 eV were estimated. These values depend on the heat treatment and the thickness of the sample. Highly conductive indium tin oxide thin films (rho = 7.4 x 10(-5) Omega cm) were obtained after RTA treatment in an open atmosphere. Such films could be used to manufacture transparent contact electrodes for solar cells.

In this work we prepared films of amorphous germanium nanoparticles embedded in SiO2 deposited by magnetron sputtering on Si and quartz heated substrates at 300, 400 and 500 degrees C. Structure, morphology, optical, electrical and photoconduction properties of all films were investigated. The Ge concentration in the depth of the films is strongly dependent on the deposition temperature. In the films deposited at 300 degrees C, the Ge content is constant in the depth, while films deposited at 500 degrees C show a significant decrease of Ge content from interface of the film with substrate towards the film free surface. From the absorption curves we obtained the Ge band gap of 1.39 eV for 300 degrees C deposited films and 1.44 eV for the films deposited at 500 degrees C. The photocurrents are higher with more than one order of magnitude than the dark ones. The photocurrent spectra present different cutoff wavelengths depending on the deposition temperature, i.e. 1325 nm for 300 degrees C and 1267 nm for 500 degrees C. These films present good responsivities of 2.42 AW(-1) (52 mu W incident power) at 300 degrees C and 0.69 AW(-1) (57 mW) at 500 degrees C and high internal quantum efficiency of similar to 445% for 300 degrees C and similar to 118% for 500 degrees C.

ZnxCo1-xFe2O4/SiO2 (x = 0, 0.25, 0.50, 0.75, 1.00) nanocomposites (NCs) have been investigated through structural, morphological and magnetic measurements. X-ray diffraction and Mossbauer data indicated the presence of nanocrystalline mixed cubic spinel. The lattice parameters gradually decreased with increasing Zn content and follow Vegard's law. The crystallite size, X-ray density and porosity of ZnxCo1-xFe2O4 decreased with increasing Zn content. The ferrite nanoparticles spherical shape and size (32.0-6.5, 17.5-8.1 and 36.2-18.6 nm for the NCs annealed at 500, 800 and 1100 degrees C, respectively) was established by transmission electron microscopy. The Mossbauer spectra showed the characteristic magnetic patterns of Co and Zn spinels. The shape of hysteresis loops revealed the dependence of superparamagnetic behavior on the structural properties. The saturation magnetization (M-s) and coercive field (H-c) were also influenced by Co substitution with Zn, showing the decrease of M-s and H-c. The replacement of magnetic Co2+ with the zero magnetic moment Zn2+ induces a gradual reduction of magnetocrystalline anisotropy and decrease of H-c. (C) 2019 Elsevier B.V. All rights reserved.

The majority of eukaryotic regulated protein turnover is performed by the proteasome, a multi-catalytic enzyme. Due to the fact that proteasome enzyme abnormal functioning was observed in different malignant cells, the proteasome is becoming a target for medical treatment. In order to evaluate the mechanisms of action of pharmaceutical compounds on proteasome enzyme inhibition, detecting and characterizing its activity is essential. An electrochemical assay that allows the monitoring of the chymotrypsin-like activity and inhibition of the 20S proteasome enzyme, based on the electrochemical detection of an electroactive compound released upon proteolysis of an adequate chymotrypsin-substrate is described. By employing differential pulse voltammetric measurement, the activity of the 20S proteasome enzyme was investigated for different incubation times of 20S with oligopeptide substrate as well as for different concentrations of substrate. Enzyme kinetic parameters were determined by voltammetry and the electrochemical assay compared with fluorescence spectroscopy. Electrochemical quartz crystal microbalance and atomic force microscopy were also used to investigate substrate interaction with the 20S proteasome and their adsorption at the electrode surface. Finally, the new electrochemical assay allowed to investigate the mechanisms of two different proteasome inhibitor drugs, bortezomib and oprozomib, underlying the applicability of the assay for understanding proteasome inhibitor action.

The annealing of crystalline defects in Si single crystals created by ion implantation at room temperature was investigated. Silicon single crystals were firstly implanted at room temperature with 1.345 MeV Au1+ ions at fluences from 1 x 10(13) to 1 x 10(14) at/cm(2) to induce damage. A second implantation at room temperature was afterwards performed with 10 MeV Co3+ ions at a fluence of 3 x 10(14) at/cm(2). All samples were analyzed afterwards by Rutherford backscattering in random and channeling geometry to assess the crystalline damage present in the surface region. The results showed a significant reduction of the degree of damage or a reduction of the size of damaged region. The morphology and local atomic structure, studied using high -resolution electron microscopy, selected area electron diffraction and high resolution X-ray diffraction confirmed the reduction of damage degree and volume caused by Au implantation after Co implantation.

Oxide dispersion-strengthened ferritic steels (ODSFSs) are promising structural materials for applications in fusion and fission power reactors, but further improvement in their (high-temperature) mechanical properties and ferrite phase stability is required. This work demonstrates that an approach to produce Fe14Cr ODSFSs with a stable ferrite phase and improved strength could involve grain size strengthening by long-term milling with a tiny amount of nitrogen. Fe-14Cr-3W-0.4Ti-0.25Y(2)O(3) powders were ball-milled up to 170 hours under an argon atmosphere. In addition to X-ray diffraction, the change in product quality during milling and upon heating was thoroughly investigated by more sensitive magnetic and thermal analysis by measuring the saturation magnetization sigma(s), coercivity H-c, Curie temperature T-c, and temperature of ferrite-austenite (alpha ->gamma) transition T-alpha ->gamma. A pronounced modification of magnetic and microstructure parameters was observed when milling over 70 hours and upon heating above 800 degrees C and was found to be generated by long-term milling with a tiny amount of nitrogen. Upon heating, the nitrogen, incorporated during milling, developed a transition region, with the decomposition of nitrides precipitated at the earlier stage of heating followed by austenite decomposition, nitrogen degassing, and microstructure refinement to a grain size of a few tenths of a nm (e.g., 28 nm by heating at 910 degrees C of 100-hour milled powder). The resulting ferrite phase with refined grains is highly stable to (further) heating. The powders milled for 70 and 100 hours containing 0.175 and 0.500 wt pct nitrogen, respectively, were consolidated at 1100 degrees C with subsequent annealing at 1050 degrees C and subjected to Vickers hardness and 3-point bending tests. The steel produced from the powder milled for 70 hours shows lower hardness, higher density (close to the theoretical value of 7.8 g/cm(3)), and fracture strain. The ductility of this ODS alloy (0.075 fracture strain) is comparable with Eurofer97 (0.075 fracture strain), whereas its strength (2070 MPa ultimate stress) is significantly higher than that of Eurofer97 (1222 MPa ultimate stress). This improvement was attributed to grain size strengthening-the refined grains (promoted by milling with nitrogen) could be effectively pinned by Y-Ti-O dispersoids.

The competition between interface barrier in the Schottky-Mott limit and polarization driven mechanism is established during gradual formation of metal (Au) - ferroelectric (BaTiO3) interface. X-ray photoelectron spectroscopy provides core level energies and valence band positions in the contact region, to monitor the band alignment from the very first stages of metal deposition on BaTiO3. The band bending at metal/ferroelectric (FE) interface is extracted from the shift of core levels (Ba 3d, Ti 2p) as a function of the metal thickness. It is shown that the interface band alignment mechanism involves a well-defined polarization orientation washing out the bending expected from the work function difference. The sudden modification of the binding energies within ferroelectric at the first 2 angstrom Au indicates that the ferroelectric compensation mechanism triggered by the metal overlayer initiates already at ultrathin top layer, while subsequent growth contributes only at a gradual correction of the potential in the FE. The emerging picture is confirmed in first-principle calculation indicating the preferences of Au to grow preferentially to different terminated regions and to stabilize distinct ferroelectric polarization.

We report on the influence of dilute doping combined with the processing conditions on the morphological, structural, chemical states, photoluminescence and magnetic properties of Zn1-xNixO nanopowders. Ni doping changes the ZnO powder morphology from randomly-aggregated nanocrystals to densely-packed nanocrystals arranged in columnar particles, modifies the high-energy-component of O1 s spectrum and increases the modified Auger parameter in XPS, enhances the blue photoluminescence (PL) emission, suppresses the green PL emission and the intensity of the g = 1.997 EPR signal. Ni-ZnO nanostructures show room-temperature ferro-magnetism (implying they can serve as dilute magnetic semiconductors). The saturation magnetization, crystallite size and microstrain increase with the doping level; the c-axis constant and unit cell volume decrease, however, being unexpectedly higher with respect to a (reference) ZnO powder with a relaxed lattice. We demonstrate that the investigated properties were controlled by both (dilute) doping level and donor native defects produced by non-equilibrium (oxygen-deficiency and high rate of) ZnO formation.