National Institute Of Materials Physics - Romania

Dextran-coated zinc-doped hydroxyapatite (ZnHApD) was synthesized by an adapted sol-gel method. The stability of ZnHApD nanoparticles in an aqueous solution was analyzed using ultrasonic measurements. The analysis of the evolution in time of the attenuation for each of the frequencies was performed. The X-ray diffraction (XRD) investigations exhibited that no impurity was found. The morphology, size and size distribution of the ZnHApD sample was investigated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The TEM and SEM results showed that the ZnHApD particles have an ellipsoidal shape and a narrow distribution of sizes. The cell growth and toxicity of HEK-293 cells were investigated on the ZnHApD solution for four different concentrations and analyzed after 24 and 48 h. The ZnHApD solution presented a non-toxic activity against HEK-293 cells for all analyzed concentrations. The antibacterial assay revealed that all the tested microorganisms were inhibited by the ZnHApD dispersion after 24 and 48 h of incubation. It was observed that the effect of the ZnHApD solution on bacteria growth depended on the bacterial strain. The Porphyromonas gingivalis ATCC 33277 bacterial strain was the most sensitive, as a growth inhibition in the presence of 0.075 mu g/mL ZnHApD in the culture medium was observed.

The development of coenzyme Q(10) (CoQ(10)) based electrochemical sensor for the detection of oxidative stress initiators is described for the first time. The sensor relies on CoQ(10) redox properties. CoQ(10) was immobilized at the surface of glassy carbon electrodes (GCE) in combination with cyclodextrins (CD), alpha-CD or beta-CD, that ensure the formation of a well dispersed CoQ(10) film. Nanostructured thin films of CoQ(10) alone and in complexes with alpha-CD or beta-CD at the electrode surface were characterized by scanning electron microscopy (SEM) and Fourier-transformed infrared spectroscopy (FTIR), enabling to identify the morphology of the films and the interactions between the CoQ(10) and CD. Nafion (R) was used to ensure sensor stability. The optimization of the CoQ(10) sensor configuration was made by assessing CoQ(10) redox properties through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), correlated with the results obtained from SEM and FTIR characterization. Next, the sensor in the optimized configuration, GCE/alpha-CD + CoQ(10)/Nafion (R), was applied for the detection of oxidant molecules, hydrogen peroxide and the superoxide radical, through the evaluation of the CoQ(10) redox properties monitored by fixed potential chronoamperometry and square wave voltammetry (SWV). (C) 2019 Elsevier Ltd. All rights reserved.

ZnO-CuxO core-shell radial heterojunction nanowire arrays were fabricated by a straightforward approach which combine two simple, cost effective and large-scale preparation methods: (i) thermal oxidation in air of a zinc foil for obtaining ZnO nanowire arrays and (ii) radio frequency magnetron sputtering for covering the surface of the ZnO nanowires with a CuxO thin film. The structural, compositional, morphological and optical properties of the high aspect ratio ZnO-CuxO core-shell nanowire arrays were investigated. Individual ZnO-CuxO core-shell nanowires were contacted with Pt electrodes by means of electron beam lithography technique, diode behaviour being demonstrated. Further it was found that these n-p radial heterojunction diodes based on single ZnO-CuxO nanowires exhibit a change in the current under UV light illumination and therefore behaving as photodetectors.

This study proves that the new developed zinc-doped hydroxyapatite (ZnHAp) colloids by an adapted sol-gel method can be widely used in the pharmaceutical, medical, and environmental industries. ZnHAp nanoparticles were stabilized in an aqueous solution, and their colloidal dispersions have been characterized by different techniques. Scanning Electron Microscopy (SEM) was used to get information on the morphology and composition of the investigated samples. Energy-dispersive X-ray spectroscopy (EDX) analysis confirmed the elemental compositions of ZnHAp colloidal dispersions. The homogeneous and uniform distribution of constituent elements (zinc, calcium, phosphorus, oxygen) was highlighted by the obtained elemental mapping results. The X-ray diffraction (XRD) results of the obtained samples showed a single phase corresponding to the hexagonal hydroxyapatite. The characteristic bands of the hydroxyapatite structure were also evidenced by Fourier-transform infrared spectroscopy (FTIR) analysis. For a stability assessment of the colloidal system, -potential for the ZnHAp dispersions was estimated. Dynamic light scattering (DLS) was used to determine particles dispersion and hydrodynamic diameter (D-HYD). The goal of this study was to provide for the first time information on the stability of ZnHAp particles in solutions evaluated by non-destructive ultrasound-based technique. In this work, the influence of the ZnHAp colloidal solutions stability on the development of bacteria, such as Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), was also established for the first time. The antimicrobial activity of ZnHAp solutions was strongly influenced by both the stability of the solutions and the amount of Zn.

Laser melting deposition is a 3D printing method usually studied for the manufacturing of machine parts in the industry. However, for the medical sector, although feasible, applications and actual products taking advantage of this technique are only scarcely reported. Therefore, in this study, Ti6Al4V orthopedic implants in the form of plates were 3D printed by laser melting deposition. Tuning of the laser power, scanning speed and powder feed rate was conducted, in order to obtain a continuous deposition after a single laser pass and to diminish unwanted blown powder, stuck in the vicinity of the printed elements. The fabrication of bone plates is presented in detail, putting emphasis on the scanning direction, which had a decisive role in the 3D printing resolution. The printed material was investigated by optical microscopy and was found to be dense, with no visible pores or cracks. The metallographic investigations and X-ray diffraction data exposed an unusual biphasic alpha+beta structure. The energy dispersive X-ray spectroscopy revealed a composition very similar to the one of the starting powder material. The mapping of the surface showed a uniform distribution of elements, with no segregations or areas with deficient elemental distribution. The in vitro tests performed on the 3D printed Ti6Al4V samples in osteoblast-like cell cultures up to 7 days showed that the material deposited by laser melting is cytocompatible.

In this study, ZnHAp layers deposited on a Si substrate were obtained by a sol-gel spin-coating procedure. The ZnHAp solutions used to obtain the ZnHAp coatings were investigated by dynamic light scattering (DLS) analysis, zeta-potential, ultrasound measurements, and flame atomic absorption spectrometry (AAS). The average measured hydrodynamic diameter from the DLS analysis, zeta-potential, and ultrasound measurements were analyzed so as to characterize and estimate the stability of the ZnHAp nanoparticles. The AAS results confirmed the presence of zinc in the gels used in the preparation of the ZnHAp layers. The layers were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD results revealed the diffraction peaks of the hexagonal hydroxyapatite in all of the investigated samples. The morphology of the ZnHAp coatings annealed at 500 degrees C (ZnHAp-500) and 700 degrees C (ZnHAp-700), which evidenced that no fissures or cracks formed on the surface of the coatings. The biocompatibility assays indicated that the ZnHAp coatings did not present any toxicity towards the HeLa cells. Furthermore, the study regarding the cytotoxicity of the ZnHAp layers against microorganisms emphasized that ZnHAp coatings exhibited an inhibitory effect towards S. aureus bacterial cells and also towards C. albicans fungal cells.

(Y0.87-xLa0.1Zr0.03Ybx)(2)O-3 (x = 0.02, 0.04, 0.05) transparent ceramics were obtained by solid-state reaction and combined sintering procedures with La2O3 and ZrO2 as sintering additives. A method based on two-step intermediate sintering in air followed by vacuum sintering was applied in order to control the densification and grain growth of the samples during the final sintering process. The results indicate that La2O3 and ZrO2 co-additives can improve the microstructure and optical properties of Yb:Y2O3 ceramics at relatively low sintering temperature. On the other hand, the addition of Zr4+ ions leads to the formation of dispersed scattering volumes in the ceramic bodies. Transmittance of 78.8% was measured for the 2.0 at% Yb:Y2O3 ceramic sample at the wavelength of 1100 nm. The spectroscopic properties of Yb:Y2O3 ceramics were investigated at room temperature. The obtained results show that the absorption cross-section at 978 nm is in the range of 2.08 x 10(-20) to 2.36 x 10(-20) cm(2), whereas the emission cross-section at 1032 nm is similar to 1.0 x 10(-20) cm(2).

The interaction of proteins with free radicals leads, among other types of damages, to the production of stable carbonyl groups, which can be used as a quantification of oxidative stress at proteins level. The aim of this study was the development of an electrochemical sensor for the detection of carbonyl groups in proteins oxidized by reactive oxygen species. Its working principle is based on the redox properties of dinitrophenylhydrazine (DNPH). BSA was used as a model protein and its oxidation achieved through Fenton reactions. Using differential pulse voltammetry at glassy carbon electrode, the electrochemical behavior of DNPH and of the native and oxidized BSA was investigated in solution. It has been shown that the hydrazine moiety of the DNPH is the electroactive center and is responsible for carbonyl complexation. Special attention was paid to the immobilization of the DNPH in order to retain its redox properties, and this was achieved on a mixed 4-styrenesulfonic acid-nafion matrix. The sensor's surface characterization and the detection of carbonyl groups in oxidized protein were performed by voltammetry, Fourier-transformed infrared spectroscopy and scanning electron microscopy while the voltammetric results were confirmed by surface plasmon resonance measurements. It has been shown that upon interaction with carbonyl groups of the oxidized protein, the oxidation peak of the hydrazine moiety of DNPH decreases as a function of incubation time and protein concentration. The sensor sensitivity was 0.015 nmol carbonyl per mg of oxidized protein and detection limits of 50 mu g oxidized BSA and 0.75 pmol carbonyls.

The electro-oxidation mechanism of free methionine and bound within different peptide sequences was investigated by voltammetry, at glassy carbon electrode, and mass spectrometry. It is proposed that the electro-oxidation of free methionine occurs in two steps, each involving the transfer of one electron and turns pH-independent from mild acid to mild alkaline electrolytes. The first oxidation reaction leads to the formation of a cation radical stabilized either through the amino group resulting in the dehydromethionine intermediate, or by interaction with a neutral methionine molecule leading to production of a dimer cationic radical. The dehydromethionine hydrolysis gave methionine sulfoxide as final oxidation product, whereas a future oxidation of methionine dimer cation radical, i.e. the second electro-oxidation step, results in a methionine dimer dication. Moreover, at high acid media, the protonated amino group influence the electro-oxidation process to take place via proton transfer mechanism. The presence of methionine sulfoxide and of the dimer cationic radical as oxidation products of methionine was confirmed by mass spectroscopy.

Composite thin coatings of conductive polymer (polyaniline grafted lignin, PANI-LIG) embedded with aminoglycoside Gentamicin sulfate (GS) or magnetite nanoparticles loaded with GS (Fe3O4@GS) were deposited by the matrix-assisted pulsed laser evaporation (MAPLE) technique. The aim was to obtain such nanostructured coatings for titanium-based biomedical surfaces, which would induce multi-functional properties to implantable devices, such as the controlled release of the therapeutically active substance under the action of a magnetic and/or electric field. Thus, the unaltered laser transfer of the initial biomaterials was reported, and the deposited thin coatings exhibited an appropriate nanostructured surface, suitable for bone-related applications. The laser processing of PANI-LIG materials had a meaningful impact on the composites' wettability, since the contact angle values corresponding to the composite laser processed materials decreased in comparison with pristine conductive polymer coatings, indicating more hydrophilic surfaces. The corrosion resistant structures exhibited significant antimicrobial activity against Escherichia coli, Staphylococcus aureus, and Candida albicans strains. In vitro cytotoxicity studies demonstrated that the PANI-LIG-modified titanium substrates can allow growth of bone-like cells. These results encourage further assessment of this type of biomaterial for their application in controlled drug release at implantation sites by external activation.