National Institute Of Materials Physics - Romania

Five new copper(II) acrylate complexes (acr is the acrylate anion: C3H3O2) with imidazole derivatives (2-methylimidazole/2-MeIm, 5-methylimidazole/5-MeIm, 2-ethylimidazole/2-EtIm) of type: cis-[Cu(2-RIm)(2)(acr)(2)]xH(2)O ((1): R = -CH3, x = 2; (4): R = -CH2-CH3, x = 0), trans-[Cu(2-RIm)(2)(acr)(2)] ((2): R = -CH3; (5): R = -CH2-CH3) and trans-[Cu(5-RIm)(2)(acr)(2)] ((3): R = -CH3) have been prepared and characterized by elemental analysis, Fourier Transform Infrared spectrometry (FTIR), Electron Paramagnetic Resonance (EPR), electronic reflectance spectroscopy, scanning electron microscopy, and mass spectrometry. The single crystal X-ray diffraction study of complexes (2) and (5) reveals that the copper(II) ion is located on an inversion center and show elongated octahedral geometry completed by two coplanar bidentate acrylates and two unidentate imidazole derivatives displayed in trans positions. For complex (4) the single crystal X-ray diffraction shows that the copper(II) ion is in a distorted octahedral environment which can be easily confused with a trigonal prism completed by two bidentate acrylates and two unidentate imidazole derivatives displayed in cis positions. These results indicate the fact that complexes (4) and (5) are the geometric isomers of the same compound bis(acrylate)-bis(2-ethylimidazole)-copper(II). Complexes (1) and (2), as well as (4) and (5), were produced simultaneously in the reaction of the corresponding copper(II) acrylate with imidazole derivatives in methanol solution. Furthermore, in order to be able to formulate potential applications of the obtained compounds, our next goal was to investigate the in vitro antimicrobial activity of the synthesized complexes against Gram-positive and Gram-negative bacteria, as well as fungal strains, of both clinical and ecological importance (biodeterioration of historical buildings). The trans isomers (2) and (5), followed by (4) have shown the broadest range of antimicrobial activity. In case of (1) and (2) isomers, the trans isomer (2) was significantly more active than cis (1), while the cis isomer (4) proved to be more active than trans (5). Taken together, the biological evaluation results indicate that the trans (2) was the most active complex, demonstrating its potential for the development of novel antimicrobial agents, with potential applications in the biomedical and restoration of architectural monuments fields.

Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0-80mg/kg of Zn, 5.4-60mg/kg of Fe and 0.5-4.5mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.

The discovery of bioactive glasses (BGs) in the late 1960s by Larry Hench et al. was driven by the need for implant materials with an ability to bond to living tissues, which were intended to replace inert metal and plastic implants that were not well tolerated by the body. Among a number of tested compositions, the one that later became designated by the well-known trademark of 45S5 Bioglass (R) excelled in its ability to bond to bone and soft tissues. Bonding to living tissues was mediated through the formation of an interfacial bone-like hydroxyapatite layer when the bioglass was put in contact with biological fluids in vivo. This feature represented a remarkable milestone, and has inspired many other investigations aiming at further exploring the in vitro and in vivo performances of this and other related BG compositions. This paradigmatic example of a target-oriented research is certainly one of the most valuable contributions that one can learn from Larry Hench. Such a goal-oriented approach needs to be continuously stimulated, aiming at finding out better performing materials to overcome the limitations of the existing ones, including the 45S5 Bioglass (R). Its well-known that its main limitations include: (i) the high pH environment that is created by its high sodium content could turn it cytotoxic; (ii) and the poor sintering ability makes the fabrication of porous three-dimensional (3D) scaffolds difficult. All of these relevant features strongly depend on a number of interrelated factors that need to be well compromised. The selected chemical composition strongly determines the glass structure, the biocompatibility, the degradation rate, and the ease of processing (scaffolds fabrication and sintering). This manuscript presents a first general appraisal of the scientific output in the interrelated areas of bioactive glasses and glass-ceramics, scaffolds, implant coatings, and tissue engineering. Then, it gives an overview of the critical issues that need to be considered when developing bioactive glasses for healthcare applications. The aim is to provide knowledge-based tools towards guiding young researchers in the design of new bioactive glass compositions, taking into account the desired functional properties.

Here, we show that wet impregnation of ZrO2 nanoparticles with 10% and 20% Eu oxide followed by thermal anneal in air above 500 degrees C produces full stabilization of the tetragonal phase of ZrO2 without evidencing any phase separation. The bare ZrO2 nanoparticles were obtained using three synthetic methods: oil in water microemulsion, rapid hydrothermal, and citrate complexation methods. The homogeneity of the solid solutions was assessed using X-ray diffraction, Raman spectroscopy, high resolution transmission electron microscopy, and advanced luminescence spectroscopy. Our findings show that wet impregnation, which is a recognized method for obtaining surface doped oxides, can be successfully used for obtaining doped oxides in the bulk with good homogeneity at the atomic scale. The limits of characterization technique in detecting minor phases and the roles of dopant concentration and host structure in formation of phase stabilized solid solutions are also analyzed and discussed.

Chromium substituted cobalt ferrites CoFe2-xCrxO4 (x=0; 1; 1.5) were synthesized through a soft chemistry methodthe gluconate precursor route. The gluconate precursors were characterized by infrared spectroscopy (IR), ultraviolet-visible spectroscopy and thermal analysis. The spinel oxide powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), Mossbauer spectroscopy and Brunauer-Emmett-Teller N-2 adsorption-desorption analyses. XRD indicated the formation of the spinel-type phase with good crystallinity. The mean crystalline domains size decreased from 23.8 to 17.8nm with the increase in the chromium content. SEM revealed faceted particles for which the particle sizes varied significantly with the chromium content. The chromium substituted cobalt ferrites were found to have high catalytic performance.

Two mixtures of elemental nickel and titanium powders in atomic proportions of 50% Ni + 50% Ti and 32% Ni + 68% Ti, respectively, were ground for 40 hours in a high energy planetary mill. In the case of the first mixture, the mechanical alloying was totally produced, while for the second, the alloying was partial. In both mixtures, qualitative X-ray diffraction phase analysis revealed the presence of metastable phases, such as Ni HC and NiTi- R-phase. Also, the equiatomic mixture is characterized by a partially amorphous structure. 10% of each type of mixture submitted to milling was used as reinforcing element in the form of particulates for two magnesium matrix composites. They were obtained by sintering in the plasma at 590 degrees C. In the case of the reinforced with the second mixture composite, the production of new phases other than the matrix and those present in the mixture of nickel and titanium powders after milling were recorded. The electron microscopy images of the two composites have resistant, free of micropores or microcracks matrix / particulates interfaces. The Mg-10% (32 at% Ni + 68 at% Ti) composite is characterized by Vickers hardness higher than that of the composite reinforced with the equiatomic mixture.

The realization of high-beta lasers is one of the prime applications of cavity QED promising ultra-low thresholds, integrability, and reduced power consumption in the field of green photonics. In such nanolasers, spontaneous emission can play a central role even above the threshold. By going beyond rate-equation approaches, we revisit the definition of a laser threshold in terms of the input-output characteristics and the degree of coherence of the emission. We demonstrate that there are new regimes of cavity-QED lasing, realized, e.g., in high-Q nanolasers with extended gain material, for which the two can differ significantly such that coherence is reached at much higher pump powers than required to observe the thresholdlike intensity jump. Against the common perception, such devices do not benefit from high-beta factors in terms of power reduction, as a significant amount of stimulated emission is required to quieten the spontaneous emission noise.

Photo-induced effects on charging and discharging of nanocrystals (NCs) in capacitor memories with Ge NCs in an HfO2 matrix as a floating gate layer are studied. The sequence of layers HfO2/Ge-HfO2/ HfO2 was deposited on a p-Si substrate using magnetron sputtering. Well separated Ge NCs are obtained after rapid thermal annealing at 600 degrees C. The optoelectric capacitor memories were fabricated with a semi-transparent electrode on top of the structure and an Al electrode on the back side of the Si substrate. Light illumination effects on hysteresis curves were investigated using different operation modes. The hysteresis window increases by increasing the light exposure time. The spectral dependence of the hysteresis window shows the maximum contribution of the light in the wavelength range of 950-1000 nm, corresponding to both contributions from the Si substrate and from Ge NCs. The stored information about the electrical and optical pulses is also investigated in the regime of the flat band potential measurements (retention measurements). It is shown that in our memory structure, the photo-effect on the memory retention corresponds to a tunnelling transfer of negative charges from the Si substrate to Ge NCs, up to a mean value of 1.6 electrons per NC. Published by AIP Publishing.

Electrospun sub-micrometer polymer fiber mats represent an interesting substrate which can be employed as a transparent conducting electrode. Functionalization by using nanostructures represents a convenient way of increasing the range of applications. The present paper describes an electrodeposition process which can be applied for preparing ZnO nanostructures covered fibers in a straightforward manner. Poly(methyl methacrylate) fiber mats were obtained by electrospinning using metal frame collectors. Subsequent metallization by DC sputtering was used, these microstructured electrodes being thermally transferred onto glass substrates and further employed as working electrodes for the electrochemical deposition of ZnO. The transparency of the metal covered webs, a function of fiber density, is comparable to that of conventional transparent conductive oxides electrodes such as ITO. The same enhanced control of the ZnO electrodeposition process was observed for the case of the web electrodes as for the classic case of deposition on transparent conducting oxides or on metallic substrates. Structural, optical, morphological and wetting properties were investigated and correlated with the electrodeposition conditions. The photocatalytic properties of ZnO covered fibers were tested through the decomposition of methylene blue thin films under UV irradiation.

Two ZnO materials of spherical hierarchical morphologies, with hollow (ZnOHS) and solid cores (ZnOSS), were obtained through the hydrolysis of zinc acetylacetonate in 1,4-butanediol. The nature of the defects and surface reactivity for the two ZnO materials were investigated through photoluminescence, X-ray photoelectron spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy proving the coexistence of shallow and deep defects and, also, the presence of polyol byproducts adsorbed on the outer layers of the ZnO samples. The EPR spectroscopy coupled with the spin-trapping technique showed that the surface of the ZnO samples generates reactive oxygen species (ROS) like hydroxyl (OH) and singlet oxygen (O-1(2)) as well as carbon-centered radicals. The ZnO materials exhibited a wide spectrum of antimicrobial activity, being active against Gram-positive, Gram-negative, and fungi strains, both in planktonic and, more importantly, adherent groywth states. The decrease of antimicrobial efficiency in the presence of a ROS scavenger (mannitol) and the decrease of the cell viability with the ROS level suggest that one of the mechanisms that governs both the antimicrobial and cytotoxic activities on human liver cells is ROS-mediated. However, at active antimicrobial concentrations, the biocompatibility of the tested materials is very good.