National Institute Of Materials Physics - Romania

The investigation of the effect of carbon nanomaterials and lipids on the aggregation particularities of the amyloid beta/A beta(1-42) layers is important for understanding the generation mechanism of neuronal disorder and how it can be inhibited. Additionally, amyloids are nanomaterials with a wide area of potential applications from nanotechnology to biotechnology. This paper presents a study about the preparation of A beta(1-42) layer by two different methods, Langmuir-Blodgett (L-B) and drop cast (DC), on Si and Si covered by a layer of Buckminster fullerene, C-60, and on the effect of fullerene layer or/and cholesterol (Ch) on the generation of A beta(1-42) secondary structure forms, relevant for specific applications. AFM, SEM FTIR and Raman analysis offered details about the layer surface topography, morphology and particularities of the secondary structure generated in the process of A beta(1-42) molecules aggregation. This study showed that the presence of Ch inhibited the formation of fibrils in A beta(1-42) film deposited by L-B on Si covered by C-60 The structures developed during aggregation were correlated with the topography and roughness of the films. The presence of Ch determined a decrease in roughness for L-B film and increase in roughness for DC film deposited on Si covered by C-60 layer.

A hybrid direct current magnetron sputtering/high-power impulse magnetron sputtering (DCMS/HiPIMS) technique was used to improve the structural and electrical properties of single-crystal titanium carbide (TiC) thin films. The hetero-epitaxial TiC films, similar to 60 nm thick, were grown on MgO (001) substrates at temperatures ranging from 200 degrees C to 800 degrees C, by co-sputtering of Ti and C targets powered by DCMS and HiPIMS, respectively. Films' composition and the structural, morphological, and electrical properties were comparatively investigated to those of a set of samples deposited at same temperatures by reactive-DCMS (R-DCMS) in Ar/CH4 atmosphere. The composition and the FWHM of rocking curves of the films deposited by R-DCMS varied from TiC0.84 to TiC0.94 and from 1.38 degrees to 0.64 degrees, respectively, as the growth temperature increased. TiC0.94 - TiC0.96 layers were deposited by hybrid DCMS/HiPIMS method at temperatures higher than 400 degrees C, fully strained over their full thickness, with FWHM of rocking curves of about 0.13 degrees. Electrical resistivity values measured for these films were of about 155 mu Omega cm, significantly close to those corresponding to bulk TiC0.95 single crystals. The resistivity of R-DCMS films is higher by 6% to 23% in comparison with that of the DCMS/HiPIMS grown samples, depending on the growth temperature.

We investigate topological and disorder effects in non-Hermitian systems with chiral symmetry. The system under consideration consists in a finite Su-Schrieffer-Heeger chain to which two semi-infinite leads are attached. The system lacks the parity-time and time-reversal symmetries and is appropriate for the study of quantum transport properties. The complex energy spectrum is analyzed in terms of the chain-lead coupling and chiral disorder strength, and shows substantial differences between chains with even and odd number of sites. The mid-gap edge states acquire a finite lifetime and are both of topological origin or generated by a strong coupling to the leads. The disorder induces coalescence of the topological eigenvalues, associated with exceptional points and vanishing of the eigenfunction rigidity. The electron transmission coefficient is approached in the Landauer formalism, and an analytical expression for the transmission in the range of topological states is obtained. Notably, the chiral disorder in this non-Hermitian system induces unitary conductance enhancement in the topological phase. (C) 2020 Elsevier B.V. All rights reserved.

Despite extensive studies on lanthanide (Ln) doped TiO2 nanoparticles, there is still considerable uncertainty as to whether Ln reside in the bulk (either as substitutional or interstitial dopant) or on the surface. Herein, new Ln (Eu, Sm, Nd and Er) discrete substitutional centers are identified in the anatase phase using low temperature, site selective time-gated luminescence spectroscopy. The excitation wavelength spanned UV (TiO2 host absorption) to visible excitation range into Ln f-f absorption transitions. The Ln multisite distribution is described in terms of fingerprint emission/excitation spectra and emission decays. The emission of Ln centers cover the visible (Eu, Sm) to near-infrared range (Nd, Er) and display narrow emission with full width at half maximum (FWHM) as small as 0.2 nm. The role of TiO2 host in sensitization of Ln emission is emphasized for each center. We have also found that besides discrete distribution, Ln distribute continuously on closely related anatase lattice sites. In this case, the Ln emission is significantly broader, with FWHM around 20 nm and change continuously in spectral shape and intensity with the excitation wavelength. The challenges encountered while identifying the Ln centers in TiO2 and comparison with case of CeO2 and SnO2 are also discussed. (C) 2020 Elsevier B.V. All rights reserved.

Novel composite materials are being investigated for improving the energy storage performance of electrochemical capacitors. For this goal, synergistic effects via the combination of diverse types of materials are crucial. In this work, electrodes composed of reduced graphene oxide, multiwall carbon nanotubes, as well as cerium and manganese oxides were fabricated through reactive inverse matrix-assisted pulsed laser evaporation (RIMAPLE). UV-pulsed laser irradiation of frozen aqueous dispersions containing graphene oxide sheets, carbon nanotubes, and ceria nanoentities, besides manganese acetate precursor, led to the simultaneous chemical transformation and co-deposition of hybrid electrodes onto flexible metallic substrates via photothermal and photochemical processes. Thorough morphological and compositional studies of the electrodes demonstrated the laser-induced reduction of graphene oxide, besides the crystallization of a mixture of cerium and manganese oxide nanostructures decorating the carbon nanoentities during the deposition process. Electrochemical analyses revealed a remarkable improvement of performance with the combination of electrochemical double layer in the porous nanocarbon framework with pseudocapacitance from the oxide nanostructures, obtaining excellent volumetric capacitances of up to 140 F cm(-3) at 10 mV s(-1) with the combination of all four materials. The attained results are the best ones yet published regarding RIMAPLE of hybrid nanocarbon-based electrodes with micrometric thickness. Finally, symmetric electrochemical capacitors were fabricated using aqueous electrolyte, revealing excellent stability upon tens of thousands of charge-discharge cycles.

Operation of a magnetron sputtering gas aggregation cluster source in a plasma jet regime is presented. In specific experimental conditions, the plasma extends from the inside of the cluster source in the deposition chamber as a plasma jet, transporting also the nanoparticles (NPs) produced in the cluster source. The chemistry of the NP surface is modified in-flight by injecting a chemical precursor in the plasma jet, resulting in core-shell NPs. Also, the plasma jet presents a low gas temperature, safely interacting with materials sensitive to thermal degradation (like polymers). These findings prove the potential of the presented plasma jet for applications in nanotechnology.

The 17th-19th century wooden and stone churches are an iconic symbol for the Romanian national heritage, raising urgent needs for the development of efficient and ecofriendly restoration and preservation solutions. Nanotechnology has a great but largely unexplored potential in this field, providing new tools and methods to achieve higher consolidation and protection efficiency, mainly due to the ability of nanoparticles to inhibit the growth and metabolic activity of different biodeteriorating agents, including fungi. The purpose of the present study was to report for the first time on the efficiency of MgB2 materials, mainly prized for their practical superconducting properties, against a large collection of filamentous fungal strains recently isolated from biodeteriorated wooden and stone heritage objects. Four types of MgB2 powders, with a crystallite size of 42-113 nm, were tested by qualitative (on 149 strains) and quantitative (on 87 strains) assays. The cytotoxicity was evaluated by the microscopic analysis of SiHa cells morphology and Hep2 cell cycle analysis and the ecotoxicity by the Allium test. The tested filamentous fungal strains belonged to 11 different genera, and those isolated from mural paintings and wooden objects exhibited the best capacity to colonize the inert substratum. All MgB2 powders exhibited similar and relatively low minimal inhibitory concentrations (MIC) values against the Aspergillus and Penicillium isolates, which were predominated among isolates. From the tested powders, PVZ and CERAC proved to be more efficient against the strains isolated from stone and wood materials, while LTS was active against the fungal strains colonizing the mural paintings and museum objects. The cytotoxicity results indicated that the tested powders are toxic for the human cells at concentrations higher than 50 mu g/ml, but, however, the very short lifetime of these NPs prevents their accumulation in the natural environment and, thus, the occurrence of toxic effects. The tested powders proved to be ecofriendly at the active antifungal concentrations, as suggested by the phytotoxicity test results. Taken together, our results suggest the potential of the MgB2 materials for the development of environmentally safe antifungal substances, which can be used in the control of the material cultural heritage biodeterioration process.

Doping SnO2 with trivalent lanthanide (Ln) metals aiming at optical applications faces several challenges. The elastic and electrostatic misfit between bulkier Ln activators and Sn host cation induces strain in the lattice as well as defects as a result of charge-compensation. These effects can be partially healed by thermal annealing. However, dopant segregation which occurs above a certain temperature drives quenching of Ln emission. In this work, we explore Li co-doping as a vehicle to improve the luminescence of lanthanide (Eu, Sm, Er, Dy and, Tb) doped SnO2 nanoparticles. In case of substitutional Ln dopants (Eu, Sm and Er), Li enhances significantly the Ln luminescence up to 40-46 times. The luminescence enhancement induced by Li co-doping is explained by an interplay of removal of nearby oxygen vacancies (Eu, Sm), improved Ln doping homogeneity (Er) and, improved crystallinity (Eu, Sm, Er). The improved crystallinity caused by Li co-doping accounts for less than 30% of the total enhancement. In the case of surface Ln dopants (Dy and Tb), Li co-doping does not alter the Ln emission, either in shape or intensity. Only a few Dy dopants succeed to substitute for Sn in the rutile lattice as shown by single-photon counting investigations. Collectively, our results show that the extent of luminescence enhancement induced by Li co-doping depend strongly on the Ln type. In SnO2, the common mechanisms that explain the Li induced enhancement of Ln luminescence in various hosts, either contribute partially (improved crystallization) or do not contribute at all (local structure distortion).

Addition of titanium dioxide nanoparticles (TiO2 NPs) in photocatalytic paints represents a promising alternative aiming to mineralize gaseous pollutants, such as volatile organic compounds (VOCs). However, the risks of release of nanoparticles to human health and the environmental impact have to be taken carefully into account for their development. To take into account these risks, we develop a new method of TiO2 NP synthesis. Here, we report the electrostatic stabilization in aqueous medium with pyrophosphate buffers of different pH ranges followed by coating with bio-inspired molecules (lysine, deferoxamine, dopamine) and polymers (polyacrylic acid, polyethylene glycol, polydopamine) of 4-5 nm spherical photocatalytic TiO2 NPs for the development of safer-by-design photocatalytic paint. Characterization of the so-formed TiO2 nanocomposites by dynamic light scattering (DLS), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS) showed the good grafting of the ligands on the TiO2 surface and an enhanced stability in water compared to the pristine TiO2 NPs. The photocatalytic activity of the TiO2 nanocomposites was investigated by following the degradation of methylene blue (MB) under irradiation. The results showed a modulation of the photocatalytic activity (decrease or increase of the MB degradation rate) as a function of the nature/binding strength of the bio-inspired coating on the oxide surface. Finally, the most promising nanocomposites were incorporated in paints on which preliminary chalking assays were performed after storage for one year in the dark or in interior daylight.

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)(2) have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)(2) native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 degrees C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.