National Institute Of Materials Physics - Romania

Biopolymers provide versatile platforms for designing naturally-derived wound care dressings through eco-friendly pathways. Eggshell membrane (ESM), a widely available, biocompatible biopolymer based structure features a unique 3D porous interwoven fibrous protein network. The ESM was functionalized with inorganic compounds (Ag, ZnO, CuO used either separately or combined) using a straightforward deposition technique namely radio frequency magnetron sputtering. The functionalized ESMs were characterized from morphological, structural, compositional, surface chemistry, optical, cytotoxicity and antibacterial point of view. It was emphasized that functionalization with a combination of metal oxides and exposure to visible light results in a highly efficient antibacterial activity against Escherichia coli when compared to the activity of individual metal oxide components. It is assumed that this is possible due to the fact that an axial p-n junction is created by joining the two metal oxides. This structure separates into components the charge carrier pairs promoted by visible light irradiation that further can influence the generation of reactive oxygen species which ultimately are responsible for the bactericide effect. This study proves that, by employing inexpensive and environmentally friendly materials (ESM and metal oxides) and fabrication techniques (radio frequency magnetron sputtering), affordable antibacterial materials can be developed for potential applications in chronic wound healing device area.

The ubiquitin-proteasome system regulates the level of proteins within cells through controlled proteolysis. In some diseases, the system function is dysregulated turning the ubiquitin-proteasome complex into a target for drug development. The redox behavior of proteasome inhibitors, epoxyketone and boronated peptides carfilzomib, oprozomib and delanzomib was investigated by voltammetric methods using glassy carbon and boron doped diamond electrodes. It was showed that the oxidation of epoxyketone peptides carfilzomib and oprozomib occurred in one step at glassy carbon electrode surface while at boron doped diamond two consecutive charge transfer reactions due to different adsorption orientation at the electrode surface were observed. The moieties of these peptides, involved in the oxidation process, were morpholine for carfilzomib and thiazole for oprozomib. For the boronated peptide delanzomib, two irreversible and independent redox processes, oxidation at +0.80 V and reduction at -1.40 V were identified in neutral media at both electrodes. The oxidation reaction occurred at the amino group close to the pyridine moiety of delanzomib with the transfer of one electron and one proton whereas the reduction process takes place at pyridine ring in a two-electrons two-protons mechanism. Redox mechanisms were proposed and the implications on the proteasome inhibition discussed.

The matrix-assisted pulsed laser evaporation (MAPLE) technique was used for depositing thin films based on a recently developed conjugated polymer, poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPP-DTT) and fullerene C60 blends. The targets used in the MAPLE process were obtained by freezing chloroform solutions with different DPP-DTT:C60 weight ratios, with the MAPLE deposition being carried at a low laser fluence, varying the number of laser pulses. The structural, morphological, optical, and electrical properties of the DPP-DTT:C60 blend layers deposited by MAPLE were investigated in order to emphasize the influence of the DPP-DTT:C60 weight ratio and the number of laser pulses on these features. The preservation of the chemical structure of both DPP-DTT and C60 during the MAPLE deposition process is confirmed by the presence of their vibrational fingerprints in the FTIR spectra of the organic thin films. The UV-VIS and photoluminescence spectra of the obtained organic layers reveal the absorption bands attributed to DPP-DTT and the emission bands associated with C60, respectively. The morphology of the DPP-DTT:C60 blend films consists of aggregates and fibril-like structures. Regardless the DPP-DTT:C60 weight ratio and the number of laser pulses used during the MAPLE process, the current-voltage characteristics recorded, under illumination, of all structures developed on the MAPLE deposited layers evidenced a photovoltaic cell behavior. The results proved that the MAPLE emerges as a viable technique for depositing thin films based on conjugated polymers featured by a complex structure that can be further used to develop devices for applications in the solar cell area.

We report the facile and low-cost preparation as well as detailed characterization of dense arrays of passivated ferromagnetic nickel (Ni) nanotubes (NTs) vertically-supported onto solid Au-coated Si substrates. The proposed fabrication method relies on electrochemical synthesis within the nanopores of a supported anodic aluminum oxide (AAO) template and allows for fine tuning of the NTs ferromagnetic walls just by changing the cathodic reduction potential during the nanostructures' electrochemical growth. Subsequently, the experimental platform allowed further passivation of the Ni NTs with the formation of ultra-thin antiferromagnetic layers of nickel oxide (NiO). Using adequately adapted magnetic measurements, we afterwards demonstrated that the thickness of the NT walls and of the thin antiferromagneticNiO layer, strongly influences the magnetic behavior of the dense array of exchange-coupled Ni/NiO NTs. The specific magnetic properties of these hybrid ferromagnetic/antiferromagnetic nanosystems were then correlated with the morpho-structural and geometrical parameters of the NTs, as well as ultimately strengthened by additionally-implemented micromagnetic simulations. The effect of the unidirectional anisotropy strongly amplified by the cylindrical geometry of the ferromagnetic/antiferromagnetic interfaces has been investigated with the magnetic field applied both parallel and perpendicular to the NTs axis.

Nanocomposite thin films, sensitive to methane at the room temperature (25-30 degrees C), have been prepared, starting from SnSe2 powder and Zn(II)-5,10,15,20-tetrakis-(4-aminophenyl)- -porphyrin (ZnTAPP) powder, that were fully characterized by XRD, UV-VIS, FT-IR, Nuclear Magnetic Resonance (H-1-NMR and C-13-NMR), Atomic Force Microscopy (AFM), SEM and Electron Paramagnetic Resonance (EPR) techniques. Film deposition was made by drop casting from a suitable solvent for the two starting materials, after mixing them in an ultrasonic bath. The thickness of these films were estimated from SEM images, and found to be around 1.3 mu m. These thin films proved to be sensitive to a threshold methane (CH4) concentration as low as 1000 ppm, at a room temperature of about 25 degrees C, without the need for heating the sensing element. The nanocomposite material has a prompt and reproducible response to methane in the case of air, with 50% relative humidity (RH) as well. A comparison of the methane sensing performances of our new nanocomposite film with that of other recently reported methane sensitive materials is provided. It is suitable for signaling gas presence before reaching the critical lower explosion limit concentration of methane at 50,000 ppm.

Chitosan-hydroxyapatite composite layers were deposited on Si substrates in radio frequency magnetron sputtering discharges. The plasma parameters calculated from the current-voltage radio frequency-compensated Langmuir probe characteristics indicate a huge difference between the electron temperature in the plasma and at the sample holder. These findings aid in the understanding of the coagulation pattern of hydroxyapatite-chitosan macromolecules on the substrate surface. An increase in the sizes of the spherical-shape grain-like structures formed on the coating surface with the plasma electron number density was observed. The link between the chemical composition of the chitosan-hydroxyapatite composite film and the species sputtered from the target or produced by excitation/ionization mechanisms in the plasma was determined on the basis of X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and residual gas mass spectrometry analysis.

This work presents a new synthesis and characterization of Kesterite Cu2ZnSnS4 films by one step electrodeposition with free sulfurization annealing treatment at different applied potentials. This study highlights the effect of applied potential and annealing treatment on the properties of CZTS deposited films. X-ray Diffraction and Raman spectroscopy were employed to assess the structure and composition of the films elaborated at -1V, -1.1V, and -1.2V vs Saturated Calomel Electrode (SCE). The morphological and optical properties were studied using Scanning Electron microscopy and photoluminescence spectroscopy (PL), respectively. The structural properties are improved by annealing treatment, while -1.1V vs SCE was found to be the optimum applied potential to prepare the Kesterite CZTS thin film with a bandgap around 1.5 eV. (C) 2020 Elsevier B.V. All rights reserved.

Sn nanoparticles (NPs) are usually obtained by difficult chemical routes in several steps followed by thermal treatments. Here, a simple and clean method, to obtain Sn NPs directly on the substrate, is developed based on a vapor transport technique. The method is versatile, thus can be easily adjusted to obtain Sn NPs of different size, areal density and morphology, by controlling the deposition conditions. NPs are grown on Si/SiO2 substrate and characterized. Water contact angle measurements show that Sn nanoparticles increase the surface hydrophobicity by 20%. Thus, NPs cleanly obtained from a low-cost, earth-abundant, and environmentally friendly material, can be used to modulate the wettability of surfaces. (C) 2020 Elsevier B.V. All rights reserved.

Core-double shell nylon-ZnO/polypyrrole electrospun nanofibers were fabricated by combining three straightforward methods (electrospinning, sol-gel synthesis and electrodeposition). The hybrid fibrous organic-inorganic nanocomposite was obtained starting from freestanding nylon 6/6 nanofibers obtained through electrospinning. Nylon meshes were functionalized with a very thin, continuous ZnO film by a sol-gel process and thermally treated in order to increase its crystallinity. Further, the ZnO coated networks were used as a working electrode for the electrochemical deposition of a very thin, homogenous polypyrrole layer. X-ray diffraction measurements were employed for characterizing the ZnO structures while spectroscopic techniques such as FTIR and Raman were employed for describing the polypyrrole layer. An elemental analysis was performed through X-ray microanalysis, confirming the expected double shell structure. A detailed micromorphological characterization through FESEM and TEM assays evidenced the deposition of both organic and inorganic layers. Highly transparent, flexible due to the presence of the polymer core and embedding a semiconducting heterojunction, such materials can be easily tailored and integrated in functional platforms with a wide range of applications.

Post-implant infections are a major health problem, and it is well-known that treating them with conventional drugs is accompanied by many disadvantages. The development of new biomaterials with enhanced antimicrobial properties are of major interest for the scientific world. The aim of this study was to synthesize and characterize hydroxyapatite doped with Samarium (Ca10-xSmx(PO4)(6)(OH)(2), x(Sm) = 0.05, 5Sm-HAp) suspensions, pellets and coatings. The 5Sm-HAp coatings on Si substrates were obtained by rf magnetron sputtering technique. The different techniques such as ultrasound measurements, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Glow Discharge Optical Emission Spectroscopy (GDOES), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to examine the obtained coatings. The results showed that the doped Sm ions entered the structure of hydroxyapatite successfully and Sm ions was uniformly doped onto the surface of the support. The depth profile curves of Ca, P, O, H, Ce and Si elements exhibit their presence from a surface to substrate interface as function of sputtering time. XPS analysis indicated as calcium-phosphate structures enriched in Sm3+ ions. Furthermore, the antimicrobial properties of the 5Sm-HAp suspensions, targets and coatings were assessed against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923 and Candida albicans ATCC 10231. The results of the antimicrobial assays highlighted that that the samples presented a strong antimicrobial activity against the tested microbial strains. The results showed that the coatings after 48 h of incubation inhibited the growth of all tested microbial strains under the value of 0.6 Log CFU/mL. This study shows that the 5Sm-HAp samples are good candidates for the development of new antimicrobial agents.