National Institute Of Materials Physics - Romania

23

The physico-chemical properties of two anhydrous AZA forms and their interaction with typical pharmaceutical excipients were assessed by applying various methods (such as PXRD, HPLC, TG/DSC, IR, Raman, PL or UV-Vis) in order to highlight new directions for drug formulation. The stability assessment of AZA anhydrous forms I and II was performed in order to determine the risk of degradation of the active ingredient by accidental exposure to nonstandard conditions in the industrial environment, under different storage, transport or processing conditions. The benefits of form II include increased resistance to chemical degradation over a wide range of pH, but further control of storage and processing conditions is necessary to avoid polymorphic transformation into form I. The solubility assessment on the AZA solid forms in different environments that simulate the conditions of the gastrointestinal tract has the advantage of a significantly increased solubility of form II compared with the commercial form I due to the modification of the crystalline structure. In the case of capsules compared to AZA form I or II as powder, an improvement in their solubility was observed, promoted by the presence of one or more excipients in the formulation mixture.

A series of cobalt-iron mixed oxides, CoxFe3-xO4 (x = 0; 0.05; 0.1; 0.15), were synthesized by coprecipitation and tested for oxidative decarboxylation of malic acid to pyruvic or malonic acid. The characterization of catalysts was performed by different techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFT) and Ultraviolet-visible spectroscopy (UV-Vis). Among studied catalysts, Co0.15Fe2.85O4 sample (denoted Co3Fe) showed the highest malic acid conversion in oxidative decarboxylation reaction as well as the highest pyruvic acid yield. This behavior can be due to the fact that this sample has the highest content of tetrahedral Co2+ that replaces Fe3+ from octahedral position that determine an increased number of defects that play a crucial role for the malic acid conversion.

Palladium nanoparticles entrapped in porous aromatic frameworks (PAFs) or covalent organic frameworks may promote heterogeneous catalytic reactions. However, preparing such materials as active nanocatalysts usually requires additional steps for palladium entrapment and reduction. This paper reports as a new approach, a simple procedure leading to the self-entrapment of Pd nanoparticles within the PAF structure. Thus, the selected Sonogashira synthesis affords PAF-entrapped Pd nanoparticles that can catalyze the C-C Suzuki-Miyaura cross-coupling reactions. Following this new concept, PAFs were synthesized via Sonogashira cross-coupling of the tetraiodurated derivative of tetraphenyladamantane or spiro-9,9 '-bifluorene with 1,6-diethynylpyrene, then characterized them using powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, high-resolution scanning transmission electron microscopy, and textural properties (i.e., adsorption-desorption isotherms). The PAF-entrapped Pd nanocatalysts showed high catalytic activity in Suzuki-Miyaura coupling reactions (demonstrated by preserving the turnover frequency values) and stability (demonstrated by palladium leaching and recycling experiments). This new approach presents a new class of PAFs with unique structural, topological, and compositional complexities as entrapped metal nanocatalysts or for other diverse applications.

This work reports the effect of the rapid solidification technique and thermal treatment on the martensitic transformation (MT), magnetic and magnetostrictive properties on the off-stoichiometric Ni49Mn31Ga20 and Ni51Mn28Ga21 ferromagnetic shape memory ribbons. The samples were investigated by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, magnetic and magnetostrictive measurements. The temperature dependence of the X-ray phases analysis shows the presence of martensite structures, both tetragonal and monoclinic, at room temperature and allowed to study their evolution through MT. The thermal treatment induces changes in the microstructure with implications in MT and Curie temperatures evolution. The competition between the magnetization orientation and twin boundary motion within martensitic variants under magnetic field evidenced in the magnetic-strain curves was discussed and correlated with the magnetic data.

Exchange coupling in a SrFe12O19 - Fe3O4 nanocomposite magnet was explored in this study. The composition, microstructure, local structure and magnetic properties were investigated by XRD, SEM, Mossbauer spectroscopy, and SQUID magnetometry. The magnetoplumbite SrFe12O19 and spinel Fe3O4 structures were verified by X-ray diffraction. The morphology of the composite reveals the characteristics of the two components. The hyperfine parameters allowed the identification of the Wyckoff positions of the iron ions corresponding to the involved phases. The magnetic measurements of the composite, showing a single-phase-like magnetic hysteresis loop, confirmed the exchange coupling between the hard and soft magnetic phases.

NiTi cylindrical materials were obtained by spark plasma sintering at 850??C or 900??C from high purity Ni and Ti powders. These mixtures were previously processed by mechanical alloying for 8 and 15 hours. In order to increase the alloy homogeneity, the NiTi materials were subjected to post aging treatment in protective atmosphere at constant temperature 400??C and cooling in water with ice. All samples were characterized by optical microscopy, differential calorimetry (DSC), X-ray measurements (XRD) and micro/nanoindentation measurements. The results demonstrate that the NiTi materials obtained by this preparation route have good mechanical properties and can serve as a quantitative reference for the microstructure design of shape memory materials for various applications, such as the biomedical ones.

A composite material with applications in optoelectronics has been investigated. Pulsed laser deposition CdSe-doped glass film was prepared by the combinatorial deposition from two targets, namely pure CdSe and glass belonging to the 20Li(2)O-10Al(2)O(3)-7BaO-2La(2)O(3)-2ZnO-59P(2)O(5)system. Exciton peaks in the Vis domain, related to electron-hole pairs transitions from the valence band to the conduction band, were revealed in the optical absorption spectra of the CdSe-doped film. CdSe quantum dots (QDs) band gap energy depends on the CdSe quantum confinement effect. CdSe-doped film photoluminescence exhibits peaks in the red domain assigned to CdSe transitions from the excited state to the ground state. The size of CdSe nanoclusters, determined from x-ray diffraction is correlated with scanning electron microscopy-energy dispersive x-ray spectroscopy and atomic force microscopy results. Vibration modes specific both to CdSe QDs and to the vitreous network have been evidenced by Fourier transform infrared and Raman spectroscopy.

Six compounds of the types [M(dmbg)(2)]center dot nH(2)O ((1) M: Ni, n = 0; (4) M: Cu, n = 1; Hdmbg: N,N '-dimethylbiguanide) and, respectively, [ML]center dot nH(2)O (where (2) M: Ni, L: L-1, n = 0; (3) M: Ni, L: L-2, n = 0; (5) M: Cu, L: L-1, n = 0 and (6) M: Cu, L: L-2, n = 3, H2L1: ligand resulted from the condensation of (1) with ammonia and formaldehyde and H2L2: ligand resulted from the condensation of (4) with hydrazine and formaldehyde) were characterized as mononuclear species through information provided by NMR, electronic paramagnetic resonance (EPR) and UV-Vis spectroscopy as well as cyclic voltammetry. All data are consistent with macrocyclic formation by condensation. The complexes adopt a distorted square planar geometry resulting from the chelating behaviour of the corresponding ligands. The EPR spectra recorded after the addition of Cu(II) complexes into the corresponding Ni(II) complexes show a well resolved hyperfine structure with the superhyperfine pattern corresponding to four nitrogen atom donors. The cathodically shift of E-pc2 for both series can be correlated with the increased stability of the M(I) species through macrocyclic ligands. Geometry optimization studies for complexes (2), (3), (5) and (6) have further confirmed the experimental data. The pharmacokinetic computational results indicate that the complexes exhibit medium to low intestinal absorption and slow blood-brain barrier permeability but low toxicity. Their predictive pharmacodynamic profiles show that the compounds present the ability to inhibit protease activity. By corroborating the results of the in silico analysis with the experimental ones, the most promising complexes for antimicrobial applications are (1) and (2) and, respectively, (4) and (6) for the development of novel antitumour strategies.

Lanthanum orthophosphate (LaPO4) and La0.95-xCe0.05MnxPO4 (x = 0.00, 0.03, 0.10) phosphors were synthesized by a simple and cost-efficient co-precipitation method and the formation of LaPO4 nanorods with a monoclinic P21/n crystal structure was observed. X-ray diffraction pattern analysis indicated a slight distortion of the LaPO4 crystalline structure and an increase of the lattice strain as a consequence of the Mn2+ and Ce3+ dopants incorporation in the host matrix. Scanning electron microscopy revealed that the microstructure of all powders consists of agglomerations of nanorods, which are around 17 +/- 3 nm in diameter and length ranging from 100 nm to 300 nm. Electron paramagnetic resonance measurements have indicated the presence of Mn2+ in isolated species, but also as agglomerates. Ce3+ and Mn2+ doping of LaPO4 resulted also in a decrease of the band gap up to 4.70 eV compared to the un-doped sample. Because of an energy transfer effect from Ce3+ to Mn2+ ions, green emission of Mn2+ ions at around 550 nm was observed upon 275 nm excitation.