National Institute Of Materials Physics - Romania

In this study, we report on the synthesis of L-Cysteine (L-Cys)-coated magnetic iron oxide nanoparticles (NPs) loaded with doxorubicin (Dox). The Fe3O4-L-Cys-Dox NPs were extensively characterized for their compositional and morpho-structural features using EDS, SAED, XRD, FTIR and TEM. XPS, Mossbauer spectroscopy and SQUID measurements were also performed to determine the electronic and magnetic properties of the Fe3O4-L-Cys-Dox nanoparticles. Moreover, by means of a FO-SPR sensor, we evidenced and confirmed the binding of Dox to L-Cys. Biological tests on mouse (B16F10) and human (A375) metastatic melanoma cells evidenced the internalization of magnetic nanoparticles delivering Dox. Half maximum inhibitory concentration IC50 values of Fe3O4-L-Cys-Dox were determined for both cell lines: 4.26 mu g/mL for A375 and 2.74 mu g/mL for B16F10, as compared to 60.74 and 98.75 mu g/mL, respectively, for unloaded controls. Incubation of cells with Fe3O4-L-Cys-Dox modulated MAPK signaling pathway activity 3 h post-treatment and produced cell cycle arrest and increased apoptosis by 48 h. We show that within the first 2 h of incubation in physiological (pH = 7.4) media, similar to 10-15 mu M Dox/h was released from a 200 mu g/mL Fe3O4-L-Cys-Dox solution, as compared to double upon incubation in citrate solution (pH = 3), which resembles acidic environment conditions. Our results highlight the potential of Fe3O4-L-Cys-Dox NPs as efficient drug delivery vehicles in melanoma therapy.

This article's objective is the synthesis of new composites based on thermoplastic polyurethane (TPU) and TiO2 nanowires (NWs) as free-standing films, highlighting their structural and optical properties. The free-standing TPU-TiO2 NW films were prepared by a wet chemical method accompanied by a thermal treatment at 100 degrees C for 1 h, followed by air-drying for 2 h. X-ray diffraction (XRD) studies indicated that the starting commercial TiO2 NW sample contains TiO2 tetragonal anatase (A), cubic Ti0.91O (C), and orthorhombic Ti2O3 (OR), as well as monoclinic H2Ti3O7 (M). In the presence of TPU, an increase in the ratio between the intensities of the diffraction peaks at 43.4 degrees and 48 degrees belonging to the C and A phases of titanium dioxide, respectively, is reported. The increase in the intensity of the peak at 43.4 degrees is explained to be a consequence of the interaction of TiO2 NWs with PTU, which occurs when the formation of suboxides takes place. The variation in the ratio of the absorbance of the IR bands peaked at 765-771 cm(-1) and 3304-3315 cm(-1) from 4.68 to 4.21 and 3.83 for TPU and the TPU-TiO2 NW composites, respectively, with TiO2 NW concentration equal to 2 wt.% and 17 wt.%, indicated a decrease in the higher-order aggregates of TPU with a simultaneous increase in the hydrogen bonds established between the amide groups of TPU and the oxygen atoms of TiO2 NWs. The decrease in the ratio of the intensity of the Raman lines peaked at 658 cm(-1) and 635 cm(-1), which were assigned to the vibrational modes E-g in TiO2 A and E-g in H2Ti3O7 (ITiO2-A/I-H2Ti3O7), respectively, from 3.45 in TiO2 NWs to 0.94-0.96 in the TPU-TiO2 NW composites, which indicates that the adsorption of TPU onto TiO2 NWs involves an exchange reaction of TPU in the presence of TiO2 NWs, followed by the formation of new hydrogen bonds between the -NH- of the amide group and the oxygen atoms of TixO2x-mn, Ti2O3, and Ti0.91O. Photoluminescence (PL) studies highlighted a gradual decrease in the intensity of the TPU emission band, which is situated in the spectral range 380-650 nm, in the presence of TiO2 NW. After increasing the TiO2 NW concentration in the TPU-TiO2 NW composite mass from 0 wt.% to 2 wt.% and 17 wt.%, respectively, a change in the binding angle of the TPU onto the TiO2 NW surface from 12.6 degrees to 32 degrees and 45.9 degrees, respectively, took place.

Light-emissive compounds able to transfer protons, either intra-or intermolecularly in the excited state, have increasingly attracted attention, especially by structural diversification of recognized fluorophores. We report herein synthesis and structural characterization of novel 1,3,4-oxadiazole-based compounds functionalised by salicylaldehyde or o-vanillin moieties. Solution absorption and emission spectroscopy performed on the resulted compounds indicated the essential influence of the established (intra and/or intermolecular) hydrogen bonds onto the optical properties. Theoretical calculations positively contributed to the effort of understanding the emissive behaviour of the compounds and the calculated data correlated very well to experiments. Occurrence of hydrogen bond interactions has been also observed in solid state and we discuss their molecular structures and the effects on the luminescent behaviour. The phenol groups in close proximity of the oxadiazole core were further exploited in cocrystallization experiments with pyridine-based co-partners. Hydrogen bonding were also found responsible for the supramolecular recognition between the two components. One type of the resulted co -crystals preserved the luminescence of the starting compound.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O-3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties-piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of similar to 50%), which yielded a promising compressive strength of similar to 20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

In this paper, the stability of magnesium-doped hydroxyapatite/chitosan (MHC) suspension obtained with the sol-gel approach was evaluated using nondestructive ultrasound measurements. The MHC coatings obtained by the spin-coating technique were characterized before and after immersion for 7 and 14 days, respectively, in Dulbecco's modified eagle medium (DMEM) by scanning electron microscopy, equipped with an EDAX detector. Also, the functional groups present on the MHC coatings surface were analyzed with the aid of attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy. The surface microstructure was evaluated using two commentary techniques, namely atomic force microscopy (AFM) and metallographic microscopy (MM). The influence of immersion in DMEM on the biological properties was studied with in vitro studies using primary osteoblast and HCT-8 cell lines. Our results revealed that both surface morphology and chemical composition of the MHC coatings allow rapid development of a new apatite layer on their surface after immersion in DMEM. Preliminary in vitro biological studies underlined the noncytotoxic effect of the studied samples on the proliferation of primary osteoblast and HCT-8 cell lines, which makes them a promising candidate for applications in fields such as orthopedics or dentistry. The antifungal assay of the MHC coatings was assessed using Candida albicans ATCC 10231 and their results showed a good inhibitory effect. The coatings made on the basis of the MHC composite could contribute to increasing the degree of success of implants by decreasing the risk of infections and postoperative inflammation.

Usually, before being used in biomedical applications, a biomaterials' bioactivity is tested by in vitro methods that simulate similar conditions to those found in the human body. In this work, we report on the synthesis of zinc-doped hydroxyapatite-chitosan (ZnHApC) composite coatings by the vacuum deposition method. The surface microstructure and the chemical and molecular modification of the coatings before and after soaking in DMEM (Dulbecco's Modified Eagle's Medium) were studied. For this objective, techniques such as attenuated total reflection (ATR), Fourier transform infrared (FTIR) spectroscopy, metallographic microscopy (MM), and scanning electron microscopy (SEM) were applied used. Also, water contact angle measurements and swelling studies were made on ZnHApC composite coatings before and after soaking in a biological medium. The coatings' adherence to the substrate was also studied. The results of antifungal studies on ZnHApC composite coatings against the Candida albicans microbial strain reveal their good antifungal activity. The biocompatibility of the composite coatings was tested using a primary osteoblast cell line. Our results suggest that zinc-doped hydroxyapatite-chitosan samples could be used as a bioimplant material due to their enhanced bioactivity and biocompatibility.

Shape memory alloys, especially ferromagnetic shape memory alloys, are interesting new materials for the manufacturing of stents. Iron-palladium alloys in particular can be used to manufacture self-expanding temporary stents due to their optimum rate of degradation, which is between that of magnesium and pure iron, two metals commonly used in temporary stent research. In order to avoid blood clotting upon the introduction of the stent, they are often coated with anticoagulants. In this study, sulfated pectin, a heparin mimetic, was synthesized in different ways and used as coating on multiple iron-palladium alloys. The static and dynamic prothrombin time (PT) and activated partial thromboplastin time (APTT) of the prepared materials were compared to samples uncoated or coated with polyethylene glycol. While no large differences were observed in the prothrombin time measurements, the activated partial thromboplastin time increased significantly with all alloys coated with sulfated pectin. Aside from that, sulfated pectin synthesized by different methods also caused slight changes in the activated partial thromboplastin time. These findings show that iron-palladium alloys can be coated with anticoagulants to improve their utility as material for temporary stents. Sulfated pectin was characterized by nuclear magnetic resonance (NMR) and Fourier-transform infrared (FTIR) spectroscopy, and the coated alloys by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX).

As metasurfaces begin to find industrial applications there is a need to develop scalable and cost-effective fabrication techniques which offer sub-100 nm resolution while providing high throughput and large area patterning. Here we demonstrate the use of UV-Nanoimprint Lithography and Deep Reactive Ion Etching (Bosch and Cryogenic) towards this goal. Robust processes are described for the fabrication of silicon rectangular pillars of high pattern fidelity. To demonstrate the quality of the structures, metasurface lenses, which demonstrate diffraction limited focusing and close to theoretical efficiency for NIR wavelengths lambda is an element of (1.3 mu m, 1.6 mu m), are fabricated. We demonstrate a process which removes the characteristic sidewall surface roughness of the Bosch process, allowing for smooth 90-degree vertical sidewalls. We also demonstrate that the optical performance of the metasurface lenses is not affected adversely in the case of Bosch sidewall surface roughness with 45 nm indentations (or scallops). Next steps of development are defined for achieving full wafer coverage.

Zeolitic imidazole frameworks (ZIFs) and TiO2 based composites have recently attracted interest to control pathogenic microorganism growth. In this context, two novel TiO2/ZIF-67 nanocomposites were synthesized by the microwave-assisted solvothermal method using two different routes: one pot composite (OPC) and two step composite (TSC) syntheses. X-ray powder diffraction and vibrational spectroscopy data revealed the formation of crystalline ZIF-67 and disordered TiO2 in the OPC composite, while both phases were crystalline in the TSC sample. Sphere-like morphologies were obtained for both materials, as indicated by SEM and TEM images. XPS measurements showed mixed-valence Ti (Ti3+/Ti4+) and Co (Co2+/Co3+) on the surface of both materials, while EPR analysis confirmed the presence of Co2+ ions and oxygen-related defects. The results showed that TiO2 has no antimicrobial activity against Staphylococcus aureus, while the TSC has higher and the OPC has lower activity than pure ZIF-67. Highly efficient biocidal activity at a concentration of 2.5 mg mL(-1) was observed for the TSC. The difference in the antimicrobial performance of the nanocomposites can be correlated with the balance between structural order/disorder, which depends on the synthesis route used, and the material solubility. The results also indicate the release of Co ions and the ligand as a possible mechanism together with redox reactions to inactivate bacteria. Thus, this work provides simple and promising synthesis routes to obtain TiO2/ZIF-67 nanocomposites for potential use as new antimicrobial agents.

Electronic and stability properties of quasi-2D alkylammonium perovskites are investigated using density functional theory (DFT) calculations and validated experimentally on selected classes of compounds. Our analysis is focused on perovskite structures of formula (A)(2)(A ')(n-1)PbnX3n+1, with large cations A = butyl-, pentyl-, hexylammonium (BA, PA, HXA), small cations A ' = methylammonium, formamidinium, ethylammonium, guanidinium (MA, FA, EA, GA) and halogens X = I, Br, Cl. The role of the halogen ions is outlined for the band structure, stability and defect formation energies. Two opposing trends are found for the absorption efficiency versus stability, the latter being assessed with respect to possible degradation mechanisms. Experimental validation is performed on quasi-2D perovskites based on pentylammonium cations, namely: (PA)(2)PbX4 and (PA)(2)(MA)Pb2X7, synthesized by antisolvent-assisted vapor crystallization. Structural and optical analysis are inline with the DFT based calculations. In addition, the thermogravimetric analysis shows an enhanced stability of bromide and chloride based compounds, in agreement with the theoretical predictions.