National Institute Of Materials Physics - Romania

In recent years, iron oxides-based nanostructured composite materials are of particular interest for the preparation of multifunctional thin films and membranes to be used in sustainable magnetic field adsorption and photocatalysis processes, intelligent coatings, and packing or bio-medical applications. In this paper, superparamagnetic iron oxide (core)-silica (shell) nanoparticles suitable for thin films and membrane functionalization were obtained by co-precipitation and ultrasonic-assisted sol-gel methods. The comparative/combined effect of the magnetic core co-precipitation temperature (80 and 95 degrees C) and ZnO-doping of the silica shell on the photocatalytic and nano-sorption properties of the resulted composite nanoparticles were investigated by ultraviolet-visible (UV-VIS) spectroscopy monitoring the discoloration of methylene blue (MB) solution under ultraviolet (UV) irradiation and darkness, respectively. The morphology, structure, textural, and magnetic parameters of the investigated powders were evidenced by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) measurements, and saturation magnetization (vibrating sample magnetometry, VSM). The intraparticle diffusion model controlled the MB adsorption. The pseudo- and second-order kinetics described the MB photodegradation. When using SiO2-shell functionalized nanoparticles, the adsorption and photodegradation constant rates are three-four times higher than for using starting core iron oxide nanoparticles. The obtained magnetic nanoparticles (MNPs) were tested for films deposition.

In the present study, we developed chitosan/hyaluronan nanoparticles (CS/HY NPs) for tumor targeting with vinblastine sulfate (VBL), that can be directed to the CD44 transmembrane receptor, over-expressed in cancer cells. NPs were prepared by coating with HY-preformed chitosan/tripolyphosphate (CS/TPP) NPs, or by polyelectrolyte complexation of CS with HY. NPs with a mean hydrodynamic radius (R-H) of 110 nm, 12% polydispersity index and negative zeta potential values were obtained by a direct complexation process. Transmission Electron Microscopy (TEM) images showed spherical NPs with a non-homogeneous matrix, probably due to a random localization of CS and HY interacting chains. The intermolecular interactions occurring between CS and HY upon NPs formation were experimentally evidenced by micro-Raman (mu-Raman) spectroscopy, through the analysis of the spectral changes of characteristic vibrational bands of HY during NP formation, in order to reveal the involvement of specific chemical groups in the process. Optimized NP formulation efficiently encapsulated VBL, producing a drug sustained release for 20 h. In vitro studies demonstrated a fast internalization of labeled CS/HY NPs (within 6 h) on K-562 human myeloid leukemia cells. Pre-saturation of CD44 by free HY produced a slowing-down of NP uptake over 24 h, demonstrating the need of CD44 for the internalization of HY-based NPs.

Li-ion batteries, widely used in portable electronics, electric vehicles, and energy storage systems, are an integral element of our daily life. However, the limitation of lithium sources, which leads to high prices, prompts the search for alternatives. Recently there has been noticed a rapid interest in Na-ion batteries technology. Especially, suitable cathode structures are investigated to accumulate larger sodium ions. In this paper, the high entropy layered oxide NaMn0.2Fe0.2Co0.2Ni0.2Ti0.2O2 is presented which achieves superior electrochemical properties with a stable capacity of ca. 180 mAh g(-1). The understanding of its high performance is based on a complex study of the multiphase intercalation mechanism. The combination of advanced structural analysis by XAS, in situ XRD, TEM, and computational DFT modelling gives a new concept on the nature of O3-P3 structure reorganization. The presented experimental and theoretical evidence indicates that the P3 phase of layered oxides is energetically favourable for a lower sodium content for specific transition metal-oxide pair distance. Fundamental understanding of the nature of phase transformation is crucial for tailoring structural composition, where the desirable O3-P3 reorganization will occur, resulting in achieving high-performance cathodes.

TiO2-based mixed oxide-carbon composite supports have been suggested to provide enhanced stability for platinum (Pt) electrocatalysts in polymer electrolyte membrane (PEM) fuel cells. The addition of molybdenum (Mo) to the mixed oxide is known to increase the CO tolerance of the electrocatalyst. In this work Pt catalysts, supported on Ti1-xMoxO2-C composites with a 25/75 oxide/carbon mass ratio and prepared from different carbon materials (C: Vulcan XC-72, unmodified and functionalized Black Pearls 2000), were compared in the hydrogen oxidation reaction (HOR) and in the oxygen reduction reaction (ORR) with a commercial Pt/C reference catalyst in order to assess the influence of the support on the electrocatalytic behavior. Our aim was to perform electrochemical studies in preparation for fuel cell tests. The ORR kinetic parameters from the Koutecky-Levich plot suggested a four-electron transfer per oxygen molecule, resulting in H2O. The similarity between the Tafel slopes suggested the same reaction mechanism for electrocatalysts supported by these composites. The HOR activity of the composite-supported electrocatalysts was independent of the type of carbonaceous material. A noticeable difference in the stability of the catalysts appeared only after 5000 polarization cycles; the Black Pearl-containing sample showed the highest stability.

The use of resorbable magnesium alloys in the design of implants represents a new direction in the healthcare domain. Two main research avenues are currently explored for developing or improving metallic biomaterials: (i) increase of their corrosion resistance by designed compositional and structural modifications, and (ii) functionalization of their surfaces by coating with ceramic or polymeric layers. The main objective of this work was to comparatively assess bio-functional coatings (i.e., highly-crystallized hydroxyapatite and silica-rich glass) deposited by radio-frequency magnetron sputtering (RF-MS) on a biodegradable Mg-0.8Ca alloy (0.8 wt.% of Ca). After probing their morphology (by scanning electron microscopy) and structure (by Fourier transform infrared spectroscopy and grazing incidence X-ray diffraction), the corrosion resistance of the RF-MS coated Mg-0.8Ca substrates was electrochemically tested (in synthetic biological media with different degrees of biomimicry), and their cytocompatibility was assessed in osteoblast and fibroblast cell cultures. By collective assessment, the most promising performances, in terms of mass loss (similar to 7% after 12 days), hydrogen release rate (similar to 6 mL/cm(2) after 12 days), electrochemical corrosion parameters and cytocompatibility, were obtained for the crystalline HA coating.

An original photodetector system based on self-connected CuO-ZnO radial core-shell heterojunction nanowire arrays grown on metallic interdigitated electrodes, operating as visible-light photodetector was developed by combining simple preparation approaches. Metallic interdigitated electrodes were fabricated on Si/SiO2 substrates using a conventional photolithography process. Subsequently, a Cu layer was electrodeposited on top of the metallic interdigitated electrodes. The CuO nanowire arrays (core) were obtained by thermal oxidation in air of the Cu layer. Afterwards, a ZnO thin film (shell) was deposited by RF magnetron sputtering covering the surface of the CuO nanowires. The morphological, structural, compositional, optical, electrical and photoelectrical properties of the CuO nanowire arrays and CuO-ZnO core-shell nanowire arrays grown on metallic interdigitated electrodes were investigated. The performances of the devices were evaluated by assessing the figures of merit of the photodetectors based on self-connected CuO-ZnO core-shell heterojunction nanowire arrays grown on the metallic interdigitated electrodes. The radial p-n heterojunction formed between CuO and ZnO generates a type II band alignment that favors an efficient charge separation of photogenerated electron-hole pairs at the CuO-ZnO interface, suppressing their recombination and consequently enhancing the photoresponse and the photoresponsivity of the photodetectors. The electrical connections in the fabricated photodetector devices are made without any additional complex and time-consuming lithographic step through a self-connecting approach for CuO-ZnO core-shell heterojunction nanowire arrays grown directly onto the Ti/Pt metallic interdigitated electrodes. Therefore, the present study provides an accessible path for employing low dimensional complex structures in functional optoelectronic devices such as photodetectors.

The present study aimed to assess the feasibility of developing low-cost multipurpose iron oxide/TiO2 nanocomposites (NCs) for use in combined antitumor therapies and water treatment applications. Larger size (approximate to 100 nm) iron oxide nanoparticles (IONPs) formed magnetic core-TiO2 shell structures at high Fe/Ti ratios and solid dispersions of IONPs embedded in TiO2 matrices when the Fe/Ti ratio was low. When the size of the iron phase was comparable to the size of the crystallized TiO2 nanoparticles (approximate to 10 nm), the obtained nanocomposites consisted of randomly mixed aggregates of TiO2 and IONPs. The best inductive heating and ROS photogeneration properties were shown by the NCs synthesized at 400 degrees C which contained the minimum amount of alpha-Fe2O3 and sufficiently crystallized anatase TiO2. Their cytocompatibility was assessed on cultured human and murine fibroblast cells and analyzed in relation to the adsorption of bovine serum albumin from the culture medium onto their surface. The tested nanocomposites showed excellent cytocompatibility to human fibroblast cells. The results also indicated that the environment (i.e. phosphate buffer or culture medium) used to disperse the nanomaterials prior to performing the viability tests can have a significant impact on their cytotoxicity.

The electronic structure as well as the mechanism underlying the high-mobility two-dimensional electron gases (2DEGs) at complex oxide interfaces remain elusive. Herein, using soft X-ray angle-resolved photoemission spectroscopy (ARPES), we present the band dispersion of metallic states at buffered LaAlO3/SrTiO3 (LAO/STO) heterointerfaces where a single-unit-cell LaMnO3 (LMO) spacer not only enhances the electron mobility but also renders the electronic structure robust toward X-ray radiation. By tracing the evolution of band dispersion, orbital occupation, and electron-phonon interaction of the interfacial 2DEG, we find unambiguous evidence that the insertion of the LMO buffer strongly suppresses both the formation of oxygen vacancies as well as the electron-phonon interaction on the STO side. The latter effect makes the buffered sample different from any other STO-based interfaces and may explain the maximum mobility enhancement achieved at buffered oxide interfaces.

Single-doped [Ag, Na, iodine, naphthalene (Naph), meta-dintrobenzene (m-DNB)] and double-doped, organic-inorganic (Naph + iodine; m-DNB + iodine) benzil (Bz) crystals have been grown from melt in a Bridgman-Stockbarger configuration. All crystals have been grown in the same experimental conditions, temperature variation at the growth interface = 30 K and moving speed of the growth ampoule = 1 mm/h. These conditions have been estimated from the theoretical analysis involving the solution of the classical (conventional) Stefan problem for flat solid-liquid interface in the boundary conditions imposed by our growth system. The effect of doping on the disorder degree, photoluminescence and dielectric constant of the Bz matrix has been investigated. The disorder in the crystals increased with the increase of dopant concentration. The highest disorder was induced by the organic dopant m-DNB, whose molecules does not show an adequate geometrical similarity with Bz molecules. The position of the photoluminescence peak, both at excitation with 335 nm and 435 nm, has not been affected by the presence of dopant(s). All doped samples show Second Harmonic Generation, even those with a significant degree of disorder. The effect of the single and double-doping on the second-order ONL co-efficient was analyzed by comparison with the second-order ONL coefficient of pure Bz crystals. In the case of the double-doping, the highest second-order optical nonlinear coefficient has been evidenced in the Bz crystals simultaneously doped with m-DNB and iodine in the same concentration (1%).

The concentration of thyroxine hormone is linked to a large variety of medical conditions, where the best therapy is hormone substitution, through administration of levothyroxine (LT4) medication. Herewith, the detection of these biomolecules still lacks a simple, reliable tool, such as label-free sensors.In this work, the performances of commercial screen-printed carbon electrodes, containing different nanostructured materials (carbon nanotubes, graphene, and gold nanoparticles), used as sensors for LT4 detection, were described and compared. Electrochemical methods were used for the characterization of the nanostructure-based sensors. Several optimization steps were undertaken to achieve optimum performances for selective LT4 quantification. The redox behaviour of LT4 at sensors surface together with the interfacial changes, which occur due to the interaction between nanostructures and LT4, were studied by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Differential pulse voltammetry (DPV) was used for LT4 detection, where best performances were obtained in the presence of carbon nanotubes, with a detection limit of 30 nM.