Complex Spectroscopy Studies of Nifedipine Photodegradation.

The aim of this work is to highlight the influence of UV light on the hydrolysis reaction of nifedipine (NIF) in the presence of alkaline solutions. In this context, the photodegradation of NIF in the absence of alkaline solutions caused (a) a change in the ratio between the absorbances of three bands in the UV-VIS spectra localized at 224-240 nm, 272-276 nm and 310-340 nm, assigned to the electronic transitions of -COOCH3 groups, -NO2 groups and a heterocycle with six atoms; (b) a red-shift of the photoluminescence (PL) band from 458 nm to 477 nm, simultaneous with an increase in its intensity; (c) a decrease in the ratio of the Raman line intensities, which peaked at 1224 cm-1 and 1649 cm-1, associated with the vibrational modes of -C-C-O in the ester group and C=C stretching; and (d) a decrease in the ratio between the absorbances of the IR bands, which peaked at 1493 cm-1 and 1223 cm-1, associated with the vibrational modes of the -NO2 group and C-N stretching. These changes were explained considering the NIF photodegradation reaction, which leads to the generation of the compound 4-(2-nitrosophenyl)-2.6-dimethyl-3.5-dimethoxy carbonyl pyridine. The interaction of NIF with NaOH in the absence of UV light was demonstrated to induce changes in the vibrational mode of the -C-C-O bond in the ester group. The photodegradation of NIF after its reaction with NaOH induces significant changes highlighted in its (a) UV-VIS spectra, by the shift of the absorption band at 238 nm; (b) PL spectra, by the supraunitary value of the ratio between the emission band intensities at 394-396 nm and 450 nm; (c) Raman spectra, by the change in the ratio between the intensities of the lines that peaked at 1224 cm-1 and 1649 cm-1 from 0.61 to 0.49; and (d) FTIR spectra, by the lowered absorbance of the IR band at 1493 cm-1 assigned to the vibrational mode of the -NO2 group as a result of the generation of the nitroso compound. These changes were explained considering the hydrolysis reaction products of NIF, as the nitroso compound is converted to a lactam-type compound. The photodegradation reaction rate constants of NIF and NIF after interaction with NaOH were also reported. The decrease in thermal stability of NIF samples after interaction with NaOH, as well as of NIF after exposure to UV light compared to NIF prior to exposure to UV light, was demonstrated by thermogravimetry, and the key fragments were confirmed by mass spectrometry.

A Nanocomposite Sol-Gel Film Based on PbS Quantum Dots Embedded into an Amorphous Host Inorganic Matrix.

In this study, a sol-gel film based on lead sulfide (PbS) quantum dots incorporated into a host network was synthesized as a special nanostructured composite material with potential applications in temperature sensor systems. This work dealt with the optical, structural, and morphological properties of a representative PbS quantum dot (QD)-containing thin film belonging to the Al2O3-SiO2-P2O5 system. The film was prepared using the sol-gel method combined with the spin coating technique, starting from a precursor solution containing a suspension of PbS QDs in toluene with a narrow size distribution and coated on a glass substrate in a multilayer process, followed by annealing of each deposited layer. The size (approximately 10 nm) of the lead sulfide nanocrystallites was validated by XRD and by the quantum confinement effect based on the band gap value and by TEM results. The photoluminescence peak of 1505 nm was very close to that of the precursor PbS QD solution, which demonstrated that the synthesis route of the film preserved the optical emission characteristic of the PbS QDs. The photoluminescence of the lead sulfide QD-containing film in the near infrared domain demonstrates that this material is a promising candidate for future sensing applications in temperature monitoring.

Effect of P2O5 Content on Luminescence of Reduced Graphene-Oxide-Doped ZnO-P2O5 Nano-Structured Films Prepared via the Sol-Gel Method.

A convenient and low-cost sol-gel approach for the one-step synthesis of ZnO-P2O5-rGO nanostructures with tuned bandgap and fluorescence was investigated. The obtained hybrid nanostructures exploit the properties of zinc oxide, graphene oxide and phosphorous oxide as promising candidates for a wide range of optoelectronic applications. A predominant amorphous structure, ZnO-P2O5-rGO, containing ZnO nanorods was evidenced by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The estimated size of the ZnO nanorods in nanostructures with P2O5 was noticed to decrease when the P2O5/ZnO ratio was increased. The presence of ZnO, P2O5 and rGO was confirmed by Fourier-transform infrared spectroscopy (FTIR) and Raman investigation. P2O5 was noticed to tune the bandgap and the fluorescence emissions of the nanostructured films, as estimated by UV-Vis-NIR and fluorescence spectroscopy, respectively. The electrical measurements performed at room temperature showed that the main influence on the film's resistivity does not come from the 1% rGO doping but from the P2O5/ZnO ratio. It was found that a 10/90 molar ratio of P2O5/ZnO decreases the resistivity almost seven-fold compared with rGO-doped ZnO films.

Nanostructured PbS-Doped Inorganic Film Synthesized by Sol-Gel Route.

IV-VI semiconductor quantum dots embedded into an inorganic matrix represent nanostructured composite materials with potential application in temperature sensor systems. This study explores the optical, structural, and morphological properties of a novel PbS quantum dots (QDs)-doped inorganic thin film belonging to the Al2O3-SiO2-P2O5 system. The film was synthesized by the sol-gel method, spin coating technique, starting from a precursor solution deposited on a glass substrate in a multilayer process, followed by drying of each deposited layer. Crystalline PbS QDs embedded in the inorganic vitreous host matrix formed a nanocomposite material. Specific investigations such as X-ray diffraction (XRD), optical absorbance in the ultraviolet (UV)-visible (Vis)-near infrared (NIR) domain, NIR luminescence, Raman spectroscopy, scanning electron microscopy-energy dispersive X-ray (SEM-EDX), and atomic force microscopy (AFM) were used to obtain a comprehensive characterization of the deposited film. The dimensions of the PbS nanocrystallite phase were corroborated by XRD, SEM-EDX, and AFM results. The luminescence band from 1400 nm follows the luminescence peak of the precursor solution and that of the dopant solution. The emission of the PbS-doped film in the NIR domain is a premise for potential application in temperature sensing systems.

Correlated studies of photoluminescence, vibrational spectroscopy and mass spectrometry concerning the pantoprazole sodium photodegradation.

In this work, new optical evidences concerning the changes induced of the UV light on pantoprazole sodium (PS), in solid state and as aqueous solution, are reported by UV-VIS spectroscopy, photoluminescence (PL), Raman scattering and FTIR spectroscopy. New evidences concerning the products of the PS photodegradation pathways are reported by the correlated studies of thermogravimetry and mass spectrometry. The influence of the excipients and alkaline medium on the PS photodegradation is also studied. New aspects regarding the chemical mechanism of the PS photodegradation in the presence of the water vapor and oxygen form air and the alkaline medium are shown. Our results confirm that the PS photodegradation induced of the water vapors and oxygen from air leads to the generation of 5-difluoromethoxy-3H-benzimidazole-2-thione sodium, 5-difluoromethoxy-3H-benzimidazole sodium, 2-thiol methyl-3, 4-dimethoxypyridine and 2-hydroxymethyl-3, 4-dimethoxypyridine, while in the alkaline medium, compounds of the type of the 2-oxymethyl-3,4-dimethoxypyridine sodium salts are resulted.

Photodegradation of Azathioprine in the Presence of Sodium Thiosulfate.

The effect of sodium thiosulfate (ST) on the photodegradation of azathioprine (AZA) was analyzed by UV-VIS spectroscopy, photoluminescence (PL), FTIR spectroscopy, Raman scattering, X-ray photoelectron (XPS) spectroscopy, thermogravimetry (TG) and mass spectrometry (MS). The PL studies highlighted that as the ST concentration increased from 25 wt.% to 75 wt.% in the AZA:ST mixture, the emission band of AZA gradual downshifted to 553, 542 and 530 nm. The photodegradation process of AZA:ST induced: (i) the emergence of a new band in the 320-400 nm range in the UV-VIS spectra of AZA and (ii) a change in the intensity ratio of the photoluminescence excitation (PLE) bands in the 280-335 and 335-430 nm spectral ranges. These changes suggest the emergence of new compounds during the photo-oxidation reaction of AZA with ST. The invoked photodegradation compounds were confirmed by studies of the Raman scattering, the FTIR spectroscopy and XPS spectroscopy through: (i) the downshift of the IR band of AZA from 1336 cm-1 to 1331 cm-1, attributed to N-C-N deformation in the purine ring; (ii) the change in the intensity ratio of the Raman lines peaking at 1305 cm-1 and 1330 cm-1 from 3.45 to 4.57, as the weight of ST in the AZA:ST mixture mass increased; and (iii) the emergence of a new band in the XPS O1s spectrum peaking at 531 eV, which was associated with the C=O bond. Through correlated studies of TG-MS, the main key fragments of ST-reacted AZA are reported.

Optical Properties of Transparent Rare-Earth Doped Sol-Gel Derived Nano-Glass Ceramics.

Rare-earth doped oxyfluoride glass ceramics represent a new generation of tailorable optical materials with high potential for optical-related applications such as optical amplifiers, optical waveguides, and white LEDs. Their key features are related to the high transparency and remarkable luminescence properties, while keeping the thermal and chemical advantages of oxide glasses. Sol-gel chemistry offers a flexible synthesis approach with several advantages, such as lower processing temperature, the ability to control the purity and homogeneity of the final materials on a molecular level, and the large compositional flexibility. The review will be focused on optical properties of sol-gel derived nano-glass ceramics related to the RE-doped luminescent nanocrystals (fluorides, chlorides, oxychlorides, etc.) such as photoluminescence, up-conversion luminescence, thermoluminescence and how these properties are influenced by their specific processing, mostly focusing on the findings from our group and similar ones in the literature, along with a discussion of perspectives, potential challenges, and future development directions.

Magnetism and ε-τ Phase Transformation in MnAl-Based Nanocomposite Magnets.

Melt spun ribbons of Mn53Al45C2 and Mn52Al46C2 have been synthesized by rapid quenching of the melt with the purpose of monitoring the ε-τ phase transformation to show technologically feasible ways to increase magnetic parameters and to illustrate the viability of these alloys as the next generation of rare earth (RE)-free magnets. By differential scanning calorimetry (DSC), activation energies and temperatures of onset of the ε-τ phase transformation were obtained. Structural analysis was performed using X-ray diffraction (XRD) and the resulting XRD patterns were quantitatively assessed using full profile Rietveld-type analysis. Appropriate annealing was performed in order to enable the ε-τ phase transformation. While hcp ε-phase was found to be predominant in the as-cast samples, after appropriate annealing, the tetragonal τ-phase, the one that furnishes the relevant magnetic response, was found to be predominant with an abundance of about 90%. The data suggested a mechanism of hcp ε-phase decomposition controlled by the segregation towards the interfacial regions, having the rate of transformation governed by antiphase boundary diffusion processes. Magnetic measurements of annealed sample Mn53Al45C2, consisting of predominant tetragonal τ-phase, showed high values of magnetization and increased coercivity, consistent with an energy product of about 10 MGOe, similar with previously reported magnetization measurements, providing further insight into the realization of future class of RE-free low-cost permanent magnets.

A New Zinc Phosphate-Tellurite Glass for Magneto-Optical Applications.

This work investigates the structural, magnetic and magneto-optical properties of a new zinc phosphate-tellurite glass belonging to the 45ZnO-10Al2O3-40P2O5-5TeO2 system. The glass was prepared by a wet method of processing the starting reagents followed by suitable melting-stirring-quenching-annealing steps. Specific parameters such as density, average molecular mass, molar volume, oxygen packaging density, refractive index, molar refractivity, electronic polarizability, reflection loss, optical transmission, band gap and optical basicity have been reported together with thermal, magnetic and magneto-optical characteristics. Absorption bands appear in the blue and red visible region, while over 600 nm the glass becomes more transparent. FTIR and Raman spectra evidenced phosphate-tellurite vibration modes proving the P2O5 and TeO2 network forming role. Magnetic measurements reveal the diamagnetic character of the Te-doped glass with an additional weak ferromagnetic signal, specific to diluted ferromagnetic oxides. Positive Faraday rotation angle with monotonous decreasing value at increasing wavelength was evidenced from magneto-optical measurements. The final product is a composite material comprising of a non-crystalline vitreous phase and Te-based nanoclusters accompanied by oxygen vacancies. The metallic-like Te colloids are responsible for the dark reddish color of the glass whereas the accompanying oxygen vacancies might be responsible for the weak ferromagnetic signal persisting up to room temperature.

Towards a Correlation between Structural, Magnetic, and Luminescence Properties of CeF3:Tb3+ Nanocrystals.

In this study, we report on the structural, magnetic, and optical properties of Tb3+-doped CeF3 nanocrystals prepared via a polyol-assisted route, followed by calcination. X-ray diffraction analysis and electron microscopy investigations have shown the formation of a dominant Ce0.75F3 nanocrystalline phase (of about 99%), with a relatively uniform distribution of nanocrystals about 15 nm in size. Magnetization curves showed typical paramagnetic properties related to the presence of Ce3+ and Tb3+ ions. The magnetic susceptibility showed a weak inflexion at about 150 K, assigned to the cerium ions' crystal field splitting. Under UV light excitation of the Ce3+ ions, we observed Tb3+ green luminescence with a quantum yield of about 20%.

Influence of Reduced Graphene Oxide on the Electropolymerization of 5-amino-1-naphthol and the Interaction of 1,4-phenylene Diisothiocyanate with the Poly(5-amino-1-naphtol)/Reduced Graphene Oxide Composite.

A new composite base on reduced graphene oxide (RGO) and poly(5-amino-1-naphthol) (P5A1N) was synthesized by the electrochemical polymerization of 5-amino-1-naphthol (5A1N) in the presence of HClO4 and H4SiW12O40 onto the surface of Au electrode covered with the RGO sheets. The linear dependence of the current densities of the anodic and cathodic peaks with the scan rate of the potential range (0; 0.8) V vs. SCE, reported during electropolymerization of 5A1N, indicates an electron transfer that is controlled by diffusion. A covalent functionalization of the RGO sheets with P5A1N is argued by: (i) the simultaneous disappearance of the IR band at 1584 cm-1 and the appearance of the new IR bands at 812, 976 and 3744 cm-1, and (ii) the appearance of two Raman lines at 738 and 1428 cm-1. An application of the RGO sheets covalently functionalized with P5A1N is demonstrated to support 1,4-phenylene diisothiocyanate (PDITC), a compound used as a cross-linking agent for various biological applications. The chemical adsorption of PDITC onto the RGO sheets covalently functionalized with P5A1N, which involves the appearance of new functional groups of the type thiourea, was proven by Raman scattering and IR spectroscopy.

Probing the dielectric, piezoelectric and magnetic behavior of CoFe2O4/BNT-BT0.08 composite thin film fabricated by sol-gel and spin-coating methods.

We investigated in this paper a novel bilayer composite obtained by sol-gel and spin coating of the ferroelectric 0.92Na0.5Bi0.5TiO3-0.08BaTiO3 (abbreviated as BNT-BT0.08) and ferromagnetic CoFe2O4 phases, for miniature low-frequency magnetic sensors and piezoelectric sensors. This heterostructure, deposited on Si-Pt substrate (Si-Pt/CoFe2O4/BNT-BT0.08), was characterized using selected method such as: X-ray diffraction, dielectric spectroscopy, piezoelectric force microscopy, SQUID magnetometry, atomic force microscopy/magnetic force microscopy, and advanced methods of transmission electron microscopy. CoFe2O4/BNT-BT0.08 ferromagnetic-piezoelectric thin films show good magnetization, dielectric constant and piezoelectric response. The results of analyses and measurements reveal that this heterostructure can have applications in high-performance magnetoelectric devices at room temperature.