Dana RADU

Simonkolleite nano-platelets, with the chemical formula Zn-5(OH)(8)Cl-2 center dot H2O (ZHC), both undoped and Mndoped, were synthesized by a wet-chemical synthesis method. The physicochemical properties of the materials have been investigated using several complementary experimental techniques, including powder X-ray diffraction, specific surface area and porosity measurements, Fourier-transform infrared spectroscopy, scanning electron microscopy, X-ray Fluorescence, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectroscopy. On the one hand, the morpho-structural characteristics of the material are not significantly affected by the dopant used at low concentrations; however, the textural characteristics, specifically the specific surface area and porosity, vary with the Mn concentration. On the other hand, the cellular response of skin cells (human fibroblasts and mouse melanoma) exposed to undoped and Mn-doped ZHC was assessed, revealing a certain dependency on the Mn concentration. It was observed that the cells' response could be correlated with both the dopant concentration and the exposure time of the cells, independent of the morpho-textural characteristics of the materials. Even at the low Mn amounts used in this study, the cells' response depends on the Mn concentration, thus showing drastic cytotoxicity in human fibroblast cells at concentrations higher than 0.25 mu g/mL, irrespective of the exposure time (24 or 48 h), but showing low cytotoxicity at concentrations lower than 0.25 mu g/mL. In contrast, the presence of Mn does not drastically affect mouse melanoma cells, even at concentrations higher than 0.5 mu g/mL, but this depends on the exposure time. To our knowledge, this is the first study on the effects of Simonkolleite on skin cells, and it is of great interest considering the current and potential applications of this material in skin wound treatment and animal food supplements.

Design of composite support materials based on Sn-doped TiO2 and carbon is one of the strategies to develop corrosion-resistant and CO-tolerant Pt electrocatalysts for polymer electrolyte membrane (PEM) fuel cells. As the synthesis methodology may have crucial influence on the structural and functional properties of the composites, different preparation routes for the novel support materials are explored and compared. Ti(1-x)SnxO2-C (x: 0.1-0.3) composites with different mixed oxide/carbon ratios were prepared by two sol-gel-based synthesis routes, namely (i) the introduction of a Sn precursor after the formation of the TiO2-rutile nuclei on the carbon backbone (route A), and (ii) simultaneous introduction of Ti and Sn precursors, resulting in good mixing of the Sn- and Ti-sol before the addition of the carbon (route B). The bulk and surface microstructure of the composites and the electrocatalysts obtained by their Pt-loading were investigated in detail. The incorporation of tin into the TiO2-rutile unit cell was confirmed by X-ray powder diffraction and Raman spectroscopy; the results indicated doping levels in good accordance with the amount of tin precursor. The advantages of composites and Pt electrocatalysts obtained via synthesis route B were that they do not contain segregated Sn-0 or SnO2 phases, have a more homogeneous/uniform mixed oxide distribution over the carbon backbone, and the electrochemically active surface area values (similar to 60-80 m(2)/g(Pt)) are twice as high as those of catalysts with similar compositions synthesized by method A. A common feature of the composites prepared by routes A and B was the presence of a tin oxide-rich overlayer identified by X-ray photoelectron spectroscopy. As a consequence, the electrocatalytic behavior of the catalysts was not influenced by the Ti/Sn ratio and was mainly dependent on the synthesis method used in the preparation of composite support materials. Elemental maps confirmed the formation of areas where Pt and the Sn doping element were in atomic proximity to each other, which means a favorable interaction either for the bifunctional mechanism or the electronic ligand effect. An increase in carbon content in composite materials led to an increase in both catalytic activity and long-term stability. The results of electrochemical studies showed that Sn-containing Pt catalysts with a high carbon content (75 wt%) are the most promising for potential use both as an anode and a cathode for PEM fuel cells.

TiO2-C (carbon) hybrid materials are promising electrocatalyst supports because the presence of TiO2 results in enhanced stability. Use of new types of carbonaceous materials such as reduced graphene oxide instead of traditional active carbon provides certain benefits. Although the rutile polymorph of TiO2 seems to have the most beneficial properties in these hybrid materials, the anatase type is more frequent in TiO2-rGO composites, especially in graphite oxide (GO) derived ones, as GO has several properties which may interfere with rutile formation. To explore and evaluate these peculiarities and their influence on the composite formation, we compared TiO2-C systems formulated with GO and Black Pearls (BP) carbon. Various physicochemical methods, such as attenuated total reflection infrared (ATR-IR)-, solid state NMR-, Raman- and X-ray photoelectron spectroscopy, X-ray powder diffraction (XRD), electron microscopy, etc. were used to characterize the samples from the different stages of our multistep sol-gel synthesis. Our experiments demonstrated that utilization of GO is indeed feasible for composite preparation, although its sodium contamination has to be removed during the synthesis. On the other hand, high temperature treatment and/or solvothermal treatment during composite synthesis resulted in decomposition of the functional groups of the GO and the functional properties of the final product were similar in case of both composites. However, Pt/TiO2-GO derived sample showed higher oxygen reduction reaction activity than Pt/TiO2-BP derived one. Based on the decrease of electrochemical surface area, the stability order was the following: Pt/C (commercial) < Pt/TiO2-BP derived C < Pt/TiO2-GO derived C.

Curcumin, an important bioactive compound and natural photosensitizer, which exhibits various biological properties, was loaded into inorganic carriers MgAl/ZnAl layered double hydroxides (LDH). The supporting matrices were obtained by co-precipitation, and a surfactant was used for including the organic drug. The structural, morphological, and spectral properties of the obtained composites were followed by X-ray diffraction, FTIR, SEM, UV-Vis, and fluorescence spectroscopy in solid state and in different solvents. The prepared formulations, the curcumin-loaded carriers, were introduced in alcohol-aqueous mixtures and the effect of solvent on the spectral properties of the formulations was investigated. Interactions between the keto-enol group of the pigment and the metals in LDHs laminates as well as inter-molecular bonds between alcohols and curcumin were evidenced. As a consequence, it was concluded that the composition of the carrier as well as the nature of the solvent determine the structural changes of the formulations. MgAl-LDH in powder has better spectral characteristics in the low-energy range (UV-Vis and fluorescence) than ZnAl-LDH. Their spectra are altered when methanol and water are present in the solvent mixture. The released curcumin concentration is in the range for photosensitization applications. The results have potential utilizations in many fields such as food, pharmaceutical, and biology.

Iron oxide nanoparticles were synthesized using a vortex microfluidic system and subsequently functionalized with a primary shell of salicylic acid, recognized for its ability to increase the stability and biocompatibility of coated materials. In the second stage, the vortex platform was placed in a magnetic field to facilitate the growth and development of a porous silica shell. The selected drug for this study was micafungin, an antifungal agent well regarded for its effectiveness in combating fungal infections and identified as a priority compound by the World Health Organization (WHO). The resulting nanocomposite system was characterized using various techniques, including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic light scattering (DLS), Brunauer-Emmett-Teller (BET) analysis, UV-Vis spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The synthesis method produced nanoparticles with dimensions of 5-7 nm, highlighting the advantages of the chosen approach. A desorption profile was established using a continuous-flow, UV-Vis analysis system, indicating that the bioactive compound was released slowly; after two hours, approximately 50% of the loaded micafungin was detected in the release medium. Furthermore, the results obtained from the FT-ICR MS analysis provided molecular-level confirmation, thereby supporting the release mechanism of micafungin from the nanosystem.

Layered zinc hydroxynitrate (ZHN), with the chemical formula Zn-5 (OH)(8) (NO3)(2)center dot 2H(2)O, exhibits a range of special properties such as anion-exchange and intercalation capacity, as well as biocompatibility, making it attractive for a large variety of applications in fields from nanotechnology to healthcare and agriculture. In this study nanocrystalline ZHN doped with 1,000 ppm Mn2+ was prepared by two synthesis methods (coprecipitation and solid state reaction) using similar environment-friendly precursors. The complex morpho-structural [X-ray diffraction, scanning and transmission electron microscopy, textural analysis] and spectroscopic [Fourier transform infrared and electron paramagnetic resonance (EPR)] characterization of the two ZHN nanopowders showed similar crystalline structures with Mn2+ ions localized in the nanocrystals volume, but with differences in their morphological and textural characteristics, as well as in the doping efficiency. ZHN obtained by coprecipitation consists of larger nanoplatelets with more than two times larger specific surface area and pore volume, as well as a dopant concentration than in the ZHN sample obtained by solid state reaction. The thermal stability and the on-set of the structural phase transformation have been investigated at atomic scale with high accuracy by EPR, using Mn2+ as paramagnetic probes. The on-set of the ZHN structural phase transformation toward ZnO was observed by EPR to take place at 110 degrees C and 130 degrees C for the samples prepared by coprecipitation and solid state reaction, respectively, evidencing a manganese induced local decrease of the transformation temperature. Our results contribute to the selection of the most appropriate ZHN synthesis method for specific applications and in the development of new green, cost-effective synthesis routes for Mn2+ doped nano-ZnO.

Bulk high density MgB2 and a composite material made of a PLA matrix and MgB2 powder inclusions were in vivo tested as candidates for biodegradable materials for orthopedic implants. A rat model was used. Implants were introduced into femoral bone, in transversal and longitudinal directions. Assessment of the implant-tissue interaction was performed by X-ray imaging, X-ray computer tomography, electron microscopy, cytology, and histopathology on samples at 40 and 90 days after surgery. Both materials are biocompatible, bone and adjacent soft tissue showing good tolerance of implants. Biodegradation of MgB2 is faster than for PLA-MgB2 composite, but in both cases, it is accompanied by bone regeneration. Results suggest that use of MgB2-containing composites can promote space and time control of degradation and promotes MgB2 as a promising material for fracture repair. (c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

We report for the first time on the antimicrobial activity of MgB2 powders produced via the Reactive Liquid Infiltration (RLI) process. Samples with MgB2 wt.% ranging from 2% to 99% were obtained and characterized, observing different levels of grain aggregation and of impurity phases. Their antimicrobial activity was tested against Staphylococcus aureus ATCC BAA 1026, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853, and Candida albicans ATCC 10231. A general correlation is observed between the antibacterial activity and the MgB2 wt.%, but the sample microstructure also appears to be very important. RLI-MgB2 powders show better performances compared to commercial powders against microbial strains in the planktonic form, and their activity against biofilms is also very similar.

Goethite based nanocomposites with a different composition such as 6FeO(OH)center dot MnO(OH)center dot 0.5H(2)O (Mn-composite), xFeO(OH)center dot M(OH)(2)center dot yH(2)O (Co-composite (M: Co, x = 12, y = 3), Ni-composite (M: Ni, x = 7, y = 2)) and xFeO(OH)center dot MO center dot yH(2)O (Cu-composite (M: Cu, x = 5.5, y = 3), Zn-composite (M: Zn, x = 6, y = 1.5)) have been prepared by a soft chemical synthesis consisting in acetate hydrolysis. The data provided by Fourier transform infrared (FTIR), ultraviolet-visible-near infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR) and Mossbauer spectra account for a slight modification of all composites' physicochemical properties compared to the starting material. Powder X-ray diffraction and transmission electron microscopy (TEM) investigations revealed the secondary phase nature and presence along with that of goethite. The TEM data are also consistent with a nano rod-like morphology with a 5-10 nm width and an average length of 40 nm. The catalytic oxidation of cyclooctene with O-2 using isobutyraldehyde as reductant and acetonitrile as a solvent was performed in batch conditions for 5 h at room temperature. The selectivity for the epoxide was higher than 99% for all tested solids. The conversion of cyclooctene decreased from 55% to 4% following the same order of variance as the base/acid sites ratio: Mn-composite > Fe-composite > Co-composite > Ni-composite > Zn-composite > Cu-composite. The 6FeO(OH)center dot MnO(OH)center dot 0.5H(2)O (Mn-composite) exhibited the most promising catalytic activity in cyclooctene oxidation, which can be correlated with the redox ability of Mn(iii) combined with the increased base character of this solid. The catalytic activity of this sample decreases by 10% after several successive reaction cycles.

Undoped and neodymium doped quartz glasses were obtained by the hybrid sol-gel method. The vitrification was performed in He atmosphere. The Nd(3+) characteristic absorption bands in the UV and VIS were put into evidence. Investigations in the NIR range revealed a small amount (86 ppm) of OH(-) in the vitreous matrix. FTIR and Raman spectra exhibit the SiO(2) glass characteristic vibrations and also the characteristic vibrations of Si-OH and Si-Cl bonds. The photoluminescence peaks at 640, 920 and 1080 nm belonging to the Nd(3+) doped quartz glass were evidenced.

TiO2-C (carbon) hybrid materials are promising electrocatalyst supports because the presence of TiO2 results in enhanced stability. Use of new types of carbonaceous materials such as reduced graphene oxide instead of traditional active carbon provides certain benefits. Although the rutile polymorph of TiO2 seems to have the most beneficial properties in these hybrid materials, the anatase type is more frequent in TiO2-rGO composites, especially in graphite oxide (GO) derived ones, as GO has several properties which may interfere with rutile formation. To explore and evaluate these peculiarities and their influence on the composite formation, we compared TiO2-C systems formulated with GO and Black Pearls (BP) carbon. Various physicochemical methods, such as attenuated total reflection infrared (ATR-IR)-, solid state NMR-, Raman- and X-ray photoelectron spectroscopy, X-ray powder diffraction (XRD), electron microscopy, etc. were used to characterize the samples from the different stages of our multistep sol-gel synthesis. Our experiments demonstrated that utilization of GO is indeed feasible for composite preparation, although its sodium contamination has to be removed during the synthesis. On the other hand, high temperature treatment and/or solvothermal treatment during composite synthesis resulted in decomposition of the functional groups of the GO and the functional properties of the final product were similar in case of both composites. However, Pt/TiO2-GO derived sample showed higher oxygen reduction reaction activity than Pt/TiO2-BP derived one. Based on the decrease of electrochemical surface area, the stability order was the following: Pt/C (commercial) < Pt/TiO2-BP derived C < Pt/TiO2-GO derived C.

TiO2-C (carbon) hybrid materials are promising electrocatalyst supports because the presence of TiO2 results in enhanced stability. Use of new types of carbonaceous materials such as reduced graphene oxide instead of traditional active carbon provides certain benefits. Although the rutile polymorph of TiO2 seems to have the most beneficial properties in these hybrid materials, the anatase type is more frequent in TiO2-rGO composites, especially in graphite oxide (GO) derived ones, as GO has several properties which may interfere with rutile formation. To explore and evaluate these peculiarities and their influence on the composite formation, we compared TiO2-C systems formulated with GO and Black Pearls (BP) carbon. Various physicochemical methods, such as attenuated total reflection infrared (ATR-IR)-, solid state NMR-, Raman- and X-ray photoelectron spectroscopy, X-ray powder diffraction (XRD), electron microscopy, etc. were used to characterize the samples from the different stages of our multistep sol-gel synthesis. Our experiments demonstrated that utilization of GO is indeed feasible for composite preparation, although its sodium contamination has to be removed during the synthesis. On the other hand, high temperature treatment and/or solvothermal treatment during composite synthesis resulted in decomposition of the functional groups of the GO and the functional properties of the final product were similar in case of both composites. However, Pt/TiO2-GO derived sample showed higher oxygen reduction reaction activity than Pt/TiO2-BP derived one. Based on the decrease of electrochemical surface area, the stability order was the following: Pt/C (commercial) < Pt/TiO2-BP derived C < Pt/TiO2-GO derived C.