Publications

This work reports the design and synthesis of novel oxadiazole-decorated azobenzenes, structural analysis of the resulting compounds and behavior under light irradiation. The synthetic strategy involved constructing amino functionalized heterocyclic key intermediates which were used either to yield electrophilic diazonium salts able to react with phenol moieties or as nucleophilic partners in Bayer-Mills reaction with nitroso-substituted derivatives. The amino-derived oxadiazole intermediates were investigated by absorption and emission spectroscopy providing blue and green emitted light. The target oxadiazole-decorated azobenzenes were structurally characterized, including solid-state structures, and subsequently used in irradiation experiments in order to take advantage of the azo group known to provide photoswitching abilities. We noticed quenching of the emissive properties in presence of the azo group; however, all compounds were very stable to repeated cycles of light irradiation. In addition, according to structural diversification we could obtain half-lives of the meta stable isomers within hours to hundreds of hours range. The experimental results were very well correlated with DFT calculations. The synthesis of novel oxadiazole-decorated azobenzenes using amino functionalised heterocyclic intermediates used either to provide electrophilic diazonium salts able to react with phenols or as nucleophilic partners in Bayer-Mills reaction is reported in this work. The oxadiazole-decorated azobenzenes were used in irradiation experiments to determine the parameters that characterize a photoswitch, yielding appealing results. The experimental results were very well correlated with DFT calculations.+image

This study investigates the morphological changes induced by femtosecond (fs) laser pulses in arsenic trisulfide (As2S3) thin films and gold-arsenic trisulfide (Au\As2S3) heterostructures, grown by pulsed laser deposition (PLD). By means of a direct laser writing experimental setup, the films were systematically irradiated at various laser power and irradiation times to observe their effects on surface modifications. AFM was employed for morphological and topological characterization. Our results reveal a clear transition threshold between photoexpansion and photoevaporation phenomena under different femtosecond laser power regimes, occurring between 1 and 1.5 mW, irrespective of exposure time. Notably, the presence of a gold layer in the heterostructure minimally influenced this threshold. A maximum photoexpansion of 5.2% was obtained in As2S3 films, while the Au\As2S3 heterostructure exhibited a peak photoexpansion of 0.8%. The study also includes a comparative analysis of continuous-wave (cw) laser irradiation, confirming the efficiency of fs laser pulses in inducing photoexpansion effects.

The primary objective of this research was to develop efficient solid catalysts that can directly convert the lactic acid (LA) obtained from lignocellulosic biomass into alanine (AL) through a reductive amination process. To achieve this, various catalysts based on ruthenium were synthesized using different carriers such as multi-walled carbon nanotubes (MWCNTs), beta-zeolite, and magnetic nanoparticles (MNPs). Among these catalysts, Ru/MNP demonstrated a remarkable yield of 74.0% for alanine at a temperature of 200 degrees C. This yield was found to be superior not only to the Ru/CNT (55.7%) and Ru/BEA (6.6%) catalysts but also to most of the previously reported catalysts. The characterization of the catalysts and their catalytic results revealed that metallic ruthenium nanoparticles, which were highly dispersed on the external surface of the magnetic carrier, significantly enhanced the catalyst's ability for dehydrogenation. Additionally, the -NH2 basic sites on the catalyst further facilitated the formation of alanine by promoting the adsorption of acidic reactants. Furthermore, the catalyst could be easily separated using an external magnetic field and exhibited the potential for multiple reuses without any significant loss in its catalytic performance. These practical advantages further enhance its appeal for applications in the reductive amination of lactic acid to alanine.

For the development of memory devices for the continuous advancement of IT engineering, a good understanding of the charging-discharging mechanisms in nanocrystalline floating gate memories is crucial to overcoming the current limitations. The charging-discharging mechanism in Al2O3/Ge/Al2O3 trilayer memory structures obtained by magnetron sputtering deposition is investigated as a function of the postdeposition annealing temperature, up to 900 degrees C. The change by annealing of C-V hysteresis curves from a clockwise type at low temperatures to counterclockwise one in a sample annealed within the intermediary temperature range of 550 to 650 degrees C, and then, a return to a clockwise type for annealing within the higher temperature range of 800-900 degrees C was observed. Up to 700 degrees C, memory performances are constantly improved reaching for 600 degrees C annealed samples, a memory window of 5.6 V for voltage sweep in the range -1 to +15 V, and good retention characteristics for 650 degrees C annealed structures, in which the charge loss is only similar to 2% after 10(8) s. When the annealing temperature was increased above 700 degrees C, a rapid decrease in the memory performance takes place. The annealing-induced changes are explained based on the Ge fast diffusion and nanocrystallization process, in correlation with morphological and structural high-resolution transmission electron microscopy results.

The effect of the annealing temperature on 1% nitrogen-doped WO3 materials was studied, which were then used as electrode materials for high-performance supercapacitor (SC) devices. The supercapacitive performance of the proposed materials was strongly influenced by the doping element and the annealing temperature by directly changing the defect structure of the host material. The 1% N-doped WO3 materials annealed at different temperatures were thoroughly characterized through various characterization techniques, including electron paramagnetic resonance and photoluminescence spectroscopy, giving insight into the effect of N-doping on the defect structure and optical properties of WO3. When the WO3:N materials were used as electrode material in symmetric SCs, the doping element and the annealing temperature improved the electrochemical performance. No booster materials (such as carbon black) were used in the symmetric SC designs, showing increased specific capacitance (102 F/g) and energy density (14.6 W h/kg) values.

Polymer Dispersed Liquid Crystals (PDLC) systems were obtained using chitosan as a biopolymer matrix and the nematic liquid crystal (LC) mixture E7 in various concentrations (30, 40 and 50% E7 in chitosan). Several techniques were used to analyze the obtained films: polarizing optical microscopy (POM), IR spectroscopy (FTIR), differential scanning calorimetry (DSC) and dielectric spectroscopy (DS). FTIR spectroscopy revealed minor changes for all PDLC films, suggesting weak interactions between LC and chitosan matrix. For each sample a clear segregation of the nematic droplets could be observed by POM. DSC measurements show that the phase transitions have shifted to lower temperature values for PDLC samples with approximately 2.7 degrees C compare to pure E7. The values of alpha (fraction of LC in the droplets) for compositions of 30, 40 and 50 wt% E7 in Chitosan were 0.48, 0.55 and 0.61 respectively, that are lower than for E7/PMMA system. The qualitative and quantitative analysis of the permittivity spectra obtained by DS reveals the fact that there are no significant changes in the molecular dynamics attributed to pure LC E7 compared to the PDLC composites, leading to the conclusion of the existence of a weak interaction between the two components, fact confirmed by the findings from the FTIR results.

Electrospun nanofibres based on poly(styrene sulfonate) doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) were fabricated using a straightforward procedure which combines electrospinning, sputtering deposition and electrochemical synthesis. In general, electrospun fibre meshes based on conducting polymers are prepared by mixing the conducting polymer with a carrier polymer or chemically coverage of the fibres. In contrast, freestanding nylon 6/6 nanofibre webs were prepared through electrospinning and were coated by sputtering with gold in order to make them conductive. Further, a PEDOT:PSS layer was electrochemically deposited onto the metalized nanofibre meshes and the synthesis parameters were chosen in such a way to preserve the high active area of the fibres. The prepared material was morphologically characterized and the formation of PEDOT:PSS was also demonstrated. The PEDOT:PSS coated nanofibres revealed remarkable electrical properties (sheet resistance of about 3.5 Omega cm(-2)), similar to those of metalized nanofibres (sheet resistance around 3 Omega cm2). The in vitro studies using L929 fibroblast mouse cells showed that the bioactive material has no cytotoxic effect and allows proliferation. Moreover, after 72 h of incubation, the fibroblasts shrunk their nuclei and spread suggesting that a differentiation in myofibroblast occurs without application of any kind of external stimuli. These results will be helpful for developing efficient materials for wound healing applications that work without energy consumption.

This study reports the development of a novel biocomposite for potential applications in the environmental remediation. The hydroxyapatite/sodium bicarbonate (HAp-SB) biocomposite obtained by a cheap method could offer promising characteristics to be used in environmental applications. The obtaining of HAp-SB ceramic composites was studied with the aim of increasing the adsorption efficiency of lead ions from contaminated waters. A composite material (HAp-SB) with good crystallinity that preserves the hexagonal structure of pure hydroxyapatite was obtained. For the powder recovered after decontamination of the lead solution (PbHAp-SB), the XRD model highlighted additional maxima belonging to Ca10(PO4)5(OH)2, Ca0.805Pb4.195(PO4)(OH) and PbH2P2O7. The FTIR spectra of PbHAp-SB are similar to those of HAp-SB composites showing a broadening of the vibration peaks and a slight shift. The XPS and EDS studies illustrated the purity of the HAp-SB sample. Moreover, the presence of lead in the powder recovered after decontamination was also highlighted by XPS and EDS studies. The efficiency of HAp-SB in the adsorption of Pb2+ ions from the contaminated solution was also highlighted by ultrasound studies using double-distilled water as the reference liquid. The adsorption kinetics were investigated with the aid of Langmuir and Freundlich theoretical models. The results demonstrated that the HAp-SB ceramic composite has a strong affinity for the adsorption of Pb2+ ions from contaminated solutions. The removal efficiency of Pb2+ ions was about 92% for the initial Pb2+ concentration above 50 mg/L. The results of the cell viability and cytotoxicity studies demonstrated that HAp-SB nanoparticles did not influence negatively the HeLa cell's viability and did not induce any significant changes of the morphological features of HeLa cells after 24 h of incubation. The batch adsorption results as well as the cytotoxicity assay results suggested that the HAp-SB powder could be successfully used for the removal of Pb2+ from contaminated water.

The paper describes the chemical modification of the graphene oxide (GO) surface with glucosamine, which was conjugated to GO via a carbodiimide-mediated amidation-type reaction. The efficiency of the reaction was confirmed by FT-IR and Raman spectroscopy and elemental analysis. The elaborated functionalization significantly reduces the agglomeration of graphene oxide platelets. The interactions at the interface of GO and two types of ceramic nanoparticles (ZrO2 and Al2O3 with particle sizes of 58 nm and 158 nm, respectively) were examined by zeta potential measurements at different pH values. The viscosity of ZrO2 suspensions (35 vol% of solid loading) at 1.5 s- 1 increases from 24.8 Pas to 170.7 Pas and 142.7 Pas with the addition of GO and f-GO, respectively. The interfaces at ceramic-graphene heterostructures obtained by slip casting method have been analyzed by SEM. The investigations revealed the presence of multilayer graphene oxide and flexible single-layer f-GO within the ceramic matrix.

Undoped and Sm3+doped 45P2O5-45Na2O-2Al2O3-8BaO glasses were synthesized by the melt-quenching technique. The glass structure and luminescence properties were investigated by using Raman spectroscopy, scanning electron microscopy (SEM), spectroscopic ellipsometry, Judd-Ofelt theory and photoluminescence. Electron microscopy showed the homogeneity of samples. Raman spectroscopy revealed that the overall struc-ture of the glass was unaffected by the doping of Sm3+ and ellipsometry was used to measure the optical constants. Judd-Ofelt (JO) analysis was performed on the absorption bands of Sm3+ (4f5) and the three phenomenological parameters (omega 2, omega 4, and omega 6) were computed and then used to determine radiative properties such as the radiative transition probability (Ar), the fluorescent branching ratio (beta r), the stimulated emission cross-section (sigma e) and the radiative lifetime (tau rad). Photoluminescence (PL) spectrum showed the typical four transitions of Sm3+ at wavelengths of 564, 600, 645 and 703 nm corresponding to 4G5/2 -> 6H5/2, 6H7/2, 6H9/2 and 6H11/2, respectively. The spectroscopic quality factors omega 4/omega 6, the predicted lifetime (tau rad) calculated using the JO method and the experimentally lifetime (tau exp) for the 4G5/2level were calculated and discussed. The glass color purity is as high as 98%, which makes it a potential candidate for laser emission.