National Institute Of Materials Physics - Romania

The aim of the present study was the development of Nb-doped ITO thin films for carbon monoxide (CO) sensing applications. The detection of CO is imperious because of its high toxicity, with long-term exposure having a negative impact on human health. Using a feasible sol-gel method, the doped ITO thin films were prepared at room temperature and deposited onto various substrates (Si, SiO2/glass, and glass). The structural, morphological, and optical characterization was performed by the following techniques: X-ray diffractometry (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV/Vis/NIR spectroscopic ellipsometry (SE). The analysis revealed a crystalline structure and a low surface roughness of the doped ITO-based thin films. XTEM analysis (cross-sectional transmission electron microscopy) showed that the film has crystallites of the order of 5-10 nm and relatively large pores (around 3-5 nm in diameter). A transmittance value of 80% in the visible region and an optical band-gap energy of around 3.7 eV were found for dip-coated ITO/Nb films on SiO2/glass and glass supports. The EDX measurements proved the presence of Nb in the ITO film in a molar ratio of 3.7%, close to the intended one (4%). Gas testing measurements were carried out on the ITO undoped and doped thin films deposited on glass substrate. The presence of Nb in the ITO matrix increases the electrical signal and the sensitivity to CO detection, leading to the highest response for 2000 ppm CO concentration at working temperature of 300 degrees C.

A series of LaPO4:Ce3+/Mn2+/xZr(4+) (LPOCM:xZr(4+)) (0% <= x <= 30%) emission-tunable phosphors were synthesized by a cost-efficient co-precipitation method. The samples presented a monoclinic phase structure and a macroscopic rod-like shape. Photoluminescence (PL) and electron paramagnetic resonance spectroscopy were employed, the Zr4+ concentration-dependent excitation, emission, decay time, and energy transfer (Ce3+ -> Mn2+) being discussed in detail. Under UV-excitation of Ce3+, typical green-red PL emission is observed for the LPOCM:xZr(4+) phosphors, which is attributed to the T-4(1)(G) -> (6)A(1)(S) transition of the Mn2+ ion. The charge compensation strategy achieved the Mn2+ PL-enhancement and color-tuning effect in LPOCM:xZr(4+) phosphors. A strong blue emission with color purity of up to 97% is observed in the Ce3+ singly-doped sample. Cold white light emission can be obtained by doping 5% Zr4+ in LPOCM phosphor under UV irradiation. The corresponding CIE 1931 coordinates were inferred to be (0.309, 0.329), close to the standard white emission (0.330, 0.330). The color was tuned towards whitish-orange/red emissions for higher Zr4+ concentrations (15% and 30%). These findings indicate that the charge compensation approach can greatly improve the PL and color-tunable properties of LPOCM:xZr(4+) phosphors.

Azathioprine (AZA) is a pharmacologic immunosuppressive agent administrated in various conditions such as autoimmune disease or to prevent the rejection of organ transplantation. The mechanism of action is based on its biologically active metabolite 6-mercaptopurine (6-MP), which is converted, among others, into thioguanine nucleotides capable of incorporating into replicating DNA, which may act as a strong UV chromophore and trigger DNA oxidation. The interaction between azathioprine and DNA, before and after exposure to solar simulator radiation, was investigated using UV-vis spectrometry and differential pulse voltammetry at a glassy carbon electrode. The results indicated that the interaction of AZA with UV radiation was pH-dependent and occurred with the formation of several metabolites, which induced oxidative damage in DNA, and the formation of DNA-metabolite adducts. Moreover, the viability assays obtained for the L929 cell culture showed that both azathioprine and degraded azathioprine induced a decrease in cell proliferation.

The morphology, structure, composition, and con-duction electron properties of quasi-spherical tin nanocrystals (NCs) of 2.5 nm average diameter, with unstrained, bulk-like alpha-Sn diamond cubic structure, observed in dark cubic boron nitride (cBN) crystallites, were determined by correlated analytical high-resolution scanning transmission electron microscopy and multifrequency electron spin resonance (ESR) investigations. The narrow Lorentzian ESR line with g = 2.0028 is attributed to the conduction ESR of the alpha- Sn NCs, consistent with the temperature-and frequency-independent small g-shift and intensity reduction under high temperature (950 degrees C) vacuum annealing when the alpha-Sn NCs are thermally dissolved in the host cBN crystallites. The ESR linewidth and line intensity vs temperature dependences recorded in the 20 to 295 K range are quantitatively described considering the presence of discrete, quantum confinement-induced conduction electron energy levels with Delta QC/kB = 125 K separation, close to the theoretical value for conductive alpha-Sn NCs of 2.5 nm in diameter. The observed properties are tentatively explained with the predicted nanosize induced band-gap opening and change of band ordering from bulk alpha-Sn to small unstrained alpha-Sn NCs, resulting in a topological phase transition that also explains the predominantly s-like character of the conduction band electron orbitals.

In this work, new information concerning the optical properties of black phosphorus (BP) sheets chemically/electrochemically functionalized with diphenyl amine (DPA) and its macromolecular compound (poly(diphenylamine) (PDPA)) in the absence/presence of phosphotungstic acid (PTA) is reported. Raman scattering and FTIR spectroscopy studies indicate that the interaction of BP with PTA leads to the elimination of the PxOy layer onto the surface of the BP sheets. In the case of the chemical interaction of BP with DPA, the reaction product corresponds to DPA chemically functionalized BP sheets having an imino-phosphorane (IP) structure. The electrochemical oxidation of BP sheets chemically functionalized with DPA in the presence of PTA leads to an increase in the weight of P-N bonds as a consequence of the generation of PDPA doped with the PTA heteropolyanions, as shown by FTIR spectroscopy and Raman scattering. This process is evidenced by a shift of the Raman line from 362 cm(-1) to 378 cm(-1), assigned to the A(1g) mode. This change was explained by taking into account the compression of the layers containing P atoms, which is induced by PDPA macromolecular chains. The decrease in the intensity of the PL spectra of DPA as well as PDPA, in the presence of BP, indicates that BP acts as a PL quenching agent for these compounds. A preferential orientation of the PDPA doped with the PTA heteropolyanions on the surface of BP sheets is highlighted by the variation of the binding angle of the PDPA on the surface of BP sheets from 44.7 degrees to 39.9 degrees.

The current consumption trends of plant based functional products have encouraged researchers and industry to study the production of protein enriched bakery products as a source of protein. In the context of the circular economy, the press cakes remaining after extraction of juices/oil from plants such as sea buckthorn or hemp can be valorized as they are rich in proteins, fibers and many bioactive compounds. Their use in bread making is a good solution to enrich the nutritional value of bread. Pea protein concentrate, hemp and sea buckthorn ingredients from press cakes by-products were added to whole wheat flour in different percentages and combinations (2% pea protein concentrate; 1% pea + 2% sea buckthorn ingredients; 1% pea + 2% hemp ingredients). Bread samples were obtained through three technological methods: one phase baking process (dough), two phases (sponge and dough) and one phase with dried sourdough added directly into the dough. A control sample (100% wheat whole flour) was considered. The mixtures of whole wheat flour and plant protein ingredients were rheologically tested. The bread samples were physicochemically analyzed (protein, fat, carbohydrates, energy value) and sensory characteristics were evaluated (texture, color and overall acceptability). The changes in the physicochemical characteristics, rheology behavior, microstructure and sensory quality were evaluated and compared. The energy from protein varied from 17.26 to 19.34% which means that all the samples can be considered "a source of protein". Hardness decreased in samples with sponge and dried sourdough which reflect the importance of technology in keeping the freshness of the product. The most appreciated were the samples with pea protein concentrate, with hemp ingredient obtained through an indirect bread making process and the sample with sea buckthorn ingredient prepared through a direct bread making process using dried sourdough.

The surface physico-chemistry of metallic implants governs their successful long-term functionality for orthopedic and dentistry applications. Here, we investigated the feasibility of harmoniously combining two of the star materials currently employed in bone treatment/restoration, namely, calcium-phosphate-based bioceramics (in the form of coatings that have the capacity to enhance osseointegration) and titanium alloys (used as bulk implant materials due to their mechanical performance and lack of systemic toxicity). For the first time, bovine-bone-derived hydroxyapatite (BHA) was layered on top of Ti6Al4V substrates using powder injection laser cladding technology, and then subjected, in this first stage of the research, to an array of physical-chemical analyses. The laser processing set-up involved the conjoined modulation of the BHA-to-Ti ratio (100 wt.% and 50 wt.%) and beam power range (500-1000 W). As such, on each metallic substrate, several overlapped strips were produced and the external surface of the cladded coatings was further investigated. The morphological and compositional (SEM/EDS) evaluations exposed fully covered metallic surfaces with ceramic-based materials, without any fragmentation and with a strong metallurgical bond. The structural (XRD, micro-Raman) analyses showed the formation of calcium titanate as the main phase up to maximum 800 W, accompanied by partial BHA decomposition and the consequential advent of tetracalcium phosphate (markedly above 600 W), independent of the BHA ratio. In addition, the hydrophilic behavior of the coatings was outlined, being linked to the varied surface textures and phase dynamism that emerged due to laser power increment for both of the employed BHA ratios. Hence, this research delineates a series of optimal laser cladding technological parameters for the adequate deposition of bioceramic layers with customized functionality.

In this paper, new results on the degradation of losartan potassium (LP, (1)), in the absence and presence of excipients, which was induced by UV light, the acid character of phosphate buffer solution (PBS) and alkaline medium, respectively, are reported through correlated studies of FTIR spectroscopy, photoluminescence and dielectric spectroscopy. The photoluminescence (PL) spectra of LP and the drug marked under the name Lorista (LO) are characterized by intense emission bands, peaking at 378 nm and 380 nm, respectively, accompanied by low intensity bands with a maximum at similar to 450-460 nm. Photodegradation of LO in a solid state is evidenced by a decrease in the intensity of the PL band at 380 nm, a variation that originates both in the adsorption of water vapors from the air and in the interaction of LP with excipients such as cornstarch, silicon dioxide and cellulose. The LP-water interaction is described, taking into account the main electrical parameters, i.e., complex dielectric permittivity and electrical conductivity. Photodegradation of LP and LO also induces an increase in the intensity of the emission band, at similar to 450-460 nm. The influence of acid and alkaline medium on the LO degradation is analyzed using phosphate buffer (PBS) and NaOH solutions, respectively. In both cases, a decrease in the intensity of the PL band, at 380 nm, is reported. The intensity diminution of the PL spectra of NaOH-reacted LP and LO is the result of the formation of the photodegradation product N-methanolamide-{[2'-(1H-tetrazol-5-yl)(1,1'-biphenyl)-4-yl]methyl} (2). This compound was proven by the studies of FTIR spectroscopy achieved on LP and NaOH-reacted LP. The appearance of the IR band at 1740 cm(-1) and the increase in the absorbance in the IR band at 1423 cm(-1) indicate that the photodegradation product (2) contains the C=O and C-OH functional groups.

To obtain highly homogeneous cobalt-nickel aluminate spinels with small crystallite sizes, CoNiAl alloy thin films were primarily deposited using Laser-induced Thermionic Vacuum Arc (LTVA) as a versatile method for performing processing of multiple materials, such as alloy/composite thin films, at a nanometric scale. Following thermal annealing in air, the CoNiAl metallic thin films were transformed into ceramic oxidic (Co,Ni)Al2O4 with controlled composition and crystallinity suitable for thermal stability and chemical resistance devices. Structural analysis revealed the formation of (Co,Ni)Al2O4 from the amorphous CoNiAl alloys. The mean crystallite size of the spinels was around 15 nm. Thermal annealing induces a densification process, increasing the film thickness together with the migration process of the aluminum toward the surface of the samples. The sheet resistance changed drastically from 200-240 omega/sq to more than 10(6) omega/sq, revealing a step-by-step conversion of the metallic character of the thin film to a dielectric oxidic structure. These cermet materials can be used as inert anodes for the solid oxide fuel cells (SOFCs), which require not only high stability with respect to oxidizing gases such as oxygen, but also good electrical conductivity. These combination metal-ceramics are known as bi-layer anodes. By controlling the crystallite size and the interplay between the oxide/metal composite, a balance between stability and electrical conductivity can be achieved.

Magnetic perovskite films have promising properties for use in energy-efficient spintronic devices and magnetic refrigeration. Here, an epitaxial ferromagnetic La0.67Ba0.33Mn0.95Ti0.05O3 (LBMTO-5) thin film was grown on SrTiO3(001) single crystal substrate by pulsed laser deposition. High-resolution X-ray diffraction proved the high crystallinity of the film with tetragonal symmetry. The magnetic, magnetocaloric and magnetoresistance properties at different directions of the applied magnetic field with respect to the ab plane of the film were investigated. An in-plane uni-axial magnetic anisotropy was evidenced. The LBMTO-5 epilayer exhibits a second-order ferromagnetic-paramagnetic phase transition around 234 K together with a metal-semiconductor transition close to this Curie temperature (T-C). The magnetic entropy variation under 5 T induction of a magnetic field applied parallel to the film surface reaches a maximum of 17.27 mJ/cm(3) K. The relative cooling power is 1400 mJ/cm(3) K (53% of the reference value reported for bulk Gd) for the same applied magnetic field. Giant magnetoresistance of about 82% under 5 T is obtained at a temperature close to T-C. Defined as the difference between specific resistivity obtained under 5 T with the current flowing along the magnetic easy axis and the magnetic field oriented transversally to the current, parallel and perpendicular to the sample plane, respectively, the in-plane magneto-resistance anisotropy in 5 T is about 9% near the T-C.