Publications

A novel series of Cu(II) complexes with formula M(HLn)(ClO4)(2)center dot mH(2)O [HLn: 13-membered pentaazamacrocyclic ligand resulted from condensation ofN,N '-bis(2-aminoethyl)ethane-1,2-diamine,l-tyrosine (HL1)/l-tryptophan (HL2)/l-phenylalanine (HL3) and formaldehyde] were synthesized by one-pot method. Techniques such as ESI-MS, IR, UV-Vis and EPR spectroscopy provided data characterizing the complexes as mononuclear species. The course of thermal decomposition was followed using TG/DSC-MS analysis in air atmosphere. The TG curves showed a gradual decomposition in several stages that comprise dehydration, decomposition of perchlorate ions as well as fragmentation and oxidative degradation of the organic part. The intermediates formed after first stage of water elimination are stable on 40, 15 and 80 degrees C interval for complexes (1), (2) and (3), respectively. The compounds were tested on the eukaryotic unicellular organismSaccharomyces cerevisiae, showing variable actions in terms of toxicity, cellular uptake and capacity to alleviate growth defects associated with Cu, Zn-superoxide dismutase (SOD1) depletion.

Multifunctional Bi- and Fe-modified carbon xerogel composites (CXBiFe), with different Fe concentrations, were obtained by a resorcinol-formaldehyde sol-gel method, followed by drying in ambient conditions and pyrolysis treatment. The morphological and structural characterization performed by X-ray diffraction (XRD), Raman spectroscopy, N-2 adsorption/desorption porosimetry, scanning electron microscopy (SEM) and scanning/transmission electron microscopy (STEM) analyses, indicates the formation of carbon-based nanocomposites with integrated Bi and Fe oxide nanoparticles. At higher Fe concentrations, Bi-Fe-O interactions lead to the formation of hybrid nanostructures and off-stoichiometric Bi2Fe4O9 mullite-like structures together with an excess of iron oxide nanoparticles. To examine the effect of the Fe content on the electrochemical performance of the CXBiFe composites, the obtained powders were initially dispersed in a chitosan solution and applied on the surface of glassy carbon electrodes. Then, the multifunctional character of the CXBiFe systems is assessed by involving the obtained modified electrodes for the detection of different analytes, such as biomarkers (hydrogen peroxide) and heavy metal ions (i.e., Pb2+). The achieved results indicate a drop in the detection limit for H2O2 as Fe content increases. Even though the current results suggest that the surface modifications of the Bi phase with Fe and O impurities lower Pb2+ detection efficiencies, Pb2+ sensing well below the admitted concentrations for drinkable water is also noticed.

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)(2) have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)(2) native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 degrees C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.

The present work reports the production and key properties of the CuCrFeTiV high entropy alloy synthetized mechanical alloying and spark plasma sintering. The milled powders and the as-sintered samples were analysed through scanning electron microscopy, coupled with energy dispersive X-ray spectroscopy and particle induced X-ray emission. Magnetic properties together with electrical resistivity, thermal conductivity, specific heat differential thermal analysis were also evaluated on the consolidated samples. The powders reveal an increasing content in iron as the millings are prolonged up to 20 h. The elemental composition of the sintered alloy, determined through particle induced X-ray emission, confirms the final composition after mechanical alloying with an increase of iron and a decrease in the remaining elements. Furthermore, although the alloy presents electrical resistivity typical of a high entropy alloy, a ferromagnetic behaviour was found, consistently with major Fe content as detected in prior observations. Finally, thermal measurements show that this CuCrFeTiV entropy alloy possesses thermal properties suitable for its potential use as thermal barriers.

The equimolar oxide mixture beta-Ga2O3-alpha-Fe2O3 was subjected to high-energy ball milling (HEBM) with the aim to obtain the nanoscaled GaFeO3 ortho-ferrite. X-ray diffraction, Fe-57 Mossbauer spectroscopy, and transmission electron microscopy were used to evidence the phase structure and evolution of the equimolar nano-system beta-Ga2O3-alpha-Fe2O3 under mechanochemical activation, either as-prepared or followed by subsequent calcination. The mechanical activation was performed for 2 h to 12 h in normal atmosphere. After 12 h of HEBM, only nanoscaled (similar to 20 nm) gallium-doped alpha-Fe2O3 was obtained. The GaFeO3 structure was obtained as single phase, merely after calcination at 950 degrees C for a couple of hours, of the sample being subjected to HEBM for 12 h. This temperature is 450 degrees C lower than used in the conventional solid phase reaction to obtain gallium orthoferrite. The optical and magnetic properties of representative nanoscaled samples, revealing their multifunctional character, were presented.

Gleditsia triacanthos is an aggressive invasive species in Eastern Europe, producing a significant number of pods that could represent an inexhaustible resource of raw material for various applications. The aim of this study was to extract cellulose from the Gleditsia triacanthos pods, characterize it by spectrophotometric and UHPLC-DAD-ESI/MS analysis, and use it to fabricate a wound dressing that is multi-functionalized with phenolic compounds extracted from the leaves of the same species. The obtained cellulose microfibers (CM) were functionalized, lyophilized, and characterized by ATR-FTIR and SEM. The water absorption and retention capacity as well as the controlled release of phenolic compounds with antioxidant properties evaluated in temporal dynamics were also determined. The antimicrobial activity against reference and clinical multi-drug-resistant Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Acinetobacter baumannii, Enterobacter cloacae, Candida albicans, and Candida parapsilosis strains occurred immediately after the contact with the tested materials and was maintained for 24 h for all tested microbial strains. In conclusion, the multi-functionalized cellulose microfibers (MFCM) obtained from the reproductive organs of an invasive species can represent a promising alternative for the development of functional wound dressings with antioxidant and antimicrobial activity, as well as being a scalable example for designing cost-effective, circular bio-economy approaches to combat the accelerated spread of invasive species.

In this work, the effect of the single-walled carbon nanotubes (SWNTs) as the mixtures of metallic and semiconducting tubes (M + S-SWNTs) as well as highly separated semiconducting (S-SWNTs) and metallic (M-SWNTs) tubes on the photoluminescence (PL) of poly(3-hexyl thiophene) (P3HT) was reported. Two methods were used to prepare such composites, that is, the chemical interaction of the two constituents and the electrochemical polymerization of the 3-hexyl thiophene onto the rough Au supports modified with carbon nanotubes (CNTs). The measurements of the anisotropic PL of these composites have highlighted a significant diminution of the angle of the binding of the P3HT films electrochemical synthetized onto Au electrodes covered with M + S-SWNTs. This change was attributed to metallic tubes, as was demonstrated using the anisotropic PL measurements carried out on the P3HT/M-SWNTs and P3HT/S-SWNTs composites. Small variations in the angle of the binding were reported in the case of the composites prepared by chemical interaction of the two constituents. The proposed mechanism to explain this behavior took into account the functionalization process of CNTs with P3HT. The experimental arguments of the functionalization process of CNTs with P3HT were shown by the UV-VIS-NIR and FTIR spectroscopy as well as surface-enhanced Raman scattering (SERS). A PL quenching process of P3HT induced both in the presence of S-SWNTs and M-SWNTs was reported, too. This process origins in the various de-excitation pathways which can be developed considering the energy levels diagram of the two constituents of each studied composite.

Due to its physical and chemical properties, the n-type tungsten oxide (WO3) semiconductor is a suitable photoanode for water decomposition reaction. The responses of the photoelectrochemical PEC water-splitting properties as an effect of structural and optical changes of WO3 thin films, as well as the nature of electrolyte solutions, were studied in this work. The WO3 thins films have been obtained by pulsed laser deposition (PLD) on silicon (Si(001)) covered with platinum substrates using three different laser wavelengths. As the XRD (X-ray diffraction) and XTEM (cross-section transmission electron microscopy) analysis shows, the formation of highly crystalline monocline WO3 phase is formed for the film deposited at 1064 nm wavelength and poor crystalline phases with a large ordering anisotropy, characteristic of 2D structures for the films deposited at 355 nm and 193 nm wavelengths, respectively. The photogenerated current densities J(ph) depend on the laser wavelength, in both alkaline and acidic electrolyte. The maximum values of the photocurrent density have been obtained for the sample prepared with laser emitting at 355 nm. This behavior can be correlated with the coherent crystallized atomic ordering that appear for long distances (10-15 nm) in the (001) plane of the monoclinic WO3 phase structure films obtained at 355 nm laser wavelength. All the samples show poor current density in dark conditions and they are very stable in both acidic and alkaline solutions. The highest photocurrent density value is obtained in acidic solution for the WO3 thin film prepared by 355 nm laser (29 mA/cm(2) at 1.6 V vs. RHE (1.35 V vs. Ag/AgCl)).

In the last few decades, the intensive use of agricultural lands affected crop productivity and thus raised serious concerns due to competing demands for food to feed the ever-growing world population (projected to be 9.7 billion by 2050). In this context, the development of nanotechnology-based fertilizers for crop nutrition has been suggested as an alternative tool to overcome the drawbacks arising from the current agricultural practices. Unfortunathelly, there is little studies about the effects of nanomaterials on plants. In this study we presented the effect of hydroxyapatite (nHA) and iron oxides (nIO) nanoparticles obtained in Romania on growth and photosintesis of corn and winter wheat plants. The results show that hydroxyapatite (nHA) and iron oxides (nIO) treatments applied by watering the soil had a positive effect on the photosynthesis of maize and winter wheat plants. In the case of treatments with solutions of iron oxides a negative effect on the length of main root was observation, but a compensating effect was found by increasing root density. This and also the higher chlorophyll content. led to a positive effect on height of maize and winter wheat plants.

Commercial nanopowders of MgB2 were characterized from the viewpoint of granulometric distribution, structure, microstructure, and pH behavior in water. The powders are very different: a higher amount of the MgB2 phase with a lower tendency for agglomeration determines a higher rate of pH-increase. A higher rate of pH-increase usually produces a stronger antimicrobial activity against Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Pseudomonas aeruginosa, Candida albicans, and Candida parapsilosis reference strains. The variation of the pH-increase rate suggests the possibility of temporo-spatial control of MgB2 bioactivity, although the contribution of other factors should not be neglected. Remarkably, the efficiency of the MgB2 powders is higher against biofilms than on microbes in the planktonic state. Further, our experiments confirm the antimicrobial efficiency of MgB2 in the in vitro tests against 29 methicillin resistant clinical S. aureus isolates and 33 vancomycin resistant E. faecium/faecalis strains, but in this case the biofilms are more resistant than planktonic cells. The MgB2 treatment of infected mice led to a significant decrease of E. coli colonization in liver, spleen and peritoneal liquid and it also caused changes in the intestinal microbiota. The activity of powders on HeLa and HT-29 tumor cell lines was assessed by inverted microscopy, flow cytometry, and evaluation of the cellular cycle. MgB2 inhibits tumor cell growth influencing DNA synthesis (S-phase). The obtained results indicate that the tested powders could provide promising solutions for the development of large-spectrum multifunctional antimicrobial and anti-biofilm agents, and/or for anti-cancer therapies. (C) 2021 The Authors. Published by Elsevier B.V.