Mirela-Andreea PARASCHIV

In this work, three methods for the synthesis of composites based on poly(ortho-toluidine) (POT) and WS2 are reported: (a) the solid-state interaction (SSI) of POT with WS2 nanoparticles (NPs); (b) the in situ chemical polymerization (ICP) of ortho-toluidine (OT); and (c) the electrochemical polymerization (ECP) of OT. The preparation of WS2 sheets was performed by the ball milling of the WS2 NPs followed by ultrasonication in the solvent N,N'-dimethyl formamide. During the synthesis of the POT/WS2 composites by SSI and ICP, an additional exfoliation of the WS2 NPs was reported. In this work, we demonstrated the following: (a) the ICP method leads to POT/WS2 composites, which contain repeating units of POT in the leucoemeraldine salt (LS) state, while (b) the ECP method leads to POT/WS2 composites, which contain repeating units of POT in the emeraldine salt (ES) state. Capacitances equal to 123.5, 465.76, and 751.6 mF cm-2 in the cases of POT-ES/WS2 composites, synthesized by SSI, ICP, and ECP, respectively, were reported.

This paper tackles the influence of the functionalization of polystyrene and graphene oxide (GO) composites on the flammability characteristics. A microscale combustion calorimeter (MCC) was used to experimentally determine the heat release capacity (HRC), the specific heat release rate (HRR) and the total heat released (THR). Neural models were designed that correlate the THR with a number of parameters related to the composition and type of flame retardant used, the heating rate, the amount of residue, the HRC, the peak heat release rate (PHRR), the temperature at the peak pyrolysis rate (TPHRR) and the time elapsed until the occurrence of the peak heat release rate (Time). The best results in the training, validation and testing stages were achieved with the neural model with 9 neurons in the input layer, 40 neurons in the hidden layer and one neuron in the output layer. This model was incorporated into an optimization procedure, based on a genetic algorithm, to establish the values of the input parameters used in the training of the neural networks, in order to generate a minimum THR value, which is the output parameter. Since the synthesis of polystyrene particles with different GO concentrations is costly, this research helps to reduce the number of experimental tests and allows to determine the best GO concentration by means of neural models and genetic algorithms.

This article's objective is the synthesis of new composites based on thermoplastic polyurethane (TPU) and TiO2 nanowires (NWs) as free-standing films, highlighting their structural and optical properties. The free-standing TPU-TiO2 NW films were prepared by a wet chemical method accompanied by a thermal treatment at 100 degrees C for 1 h, followed by air-drying for 2 h. X-ray diffraction (XRD) studies indicated that the starting commercial TiO2 NW sample contains TiO2 tetragonal anatase (A), cubic Ti0.91O (C), and orthorhombic Ti2O3 (OR), as well as monoclinic H2Ti3O7 (M). In the presence of TPU, an increase in the ratio between the intensities of the diffraction peaks at 43.4 degrees and 48 degrees belonging to the C and A phases of titanium dioxide, respectively, is reported. The increase in the intensity of the peak at 43.4 degrees is explained to be a consequence of the interaction of TiO2 NWs with PTU, which occurs when the formation of suboxides takes place. The variation in the ratio of the absorbance of the IR bands peaked at 765-771 cm(-1) and 3304-3315 cm(-1) from 4.68 to 4.21 and 3.83 for TPU and the TPU-TiO2 NW composites, respectively, with TiO2 NW concentration equal to 2 wt.% and 17 wt.%, indicated a decrease in the higher-order aggregates of TPU with a simultaneous increase in the hydrogen bonds established between the amide groups of TPU and the oxygen atoms of TiO2 NWs. The decrease in the ratio of the intensity of the Raman lines peaked at 658 cm(-1) and 635 cm(-1), which were assigned to the vibrational modes E-g in TiO2 A and E-g in H2Ti3O7 (ITiO2-A/I-H2Ti3O7), respectively, from 3.45 in TiO2 NWs to 0.94-0.96 in the TPU-TiO2 NW composites, which indicates that the adsorption of TPU onto TiO2 NWs involves an exchange reaction of TPU in the presence of TiO2 NWs, followed by the formation of new hydrogen bonds between the -NH- of the amide group and the oxygen atoms of TixO2x-mn, Ti2O3, and Ti0.91O. Photoluminescence (PL) studies highlighted a gradual decrease in the intensity of the TPU emission band, which is situated in the spectral range 380-650 nm, in the presence of TiO2 NW. After increasing the TiO2 NW concentration in the TPU-TiO2 NW composite mass from 0 wt.% to 2 wt.% and 17 wt.%, respectively, a change in the binding angle of the TPU onto the TiO2 NW surface from 12.6 degrees to 32 degrees and 45.9 degrees, respectively, took place.

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.

New aspects concerning the photodegradation (PD) of ampicillin are reported by photoluminescence (PL), Raman scattering and FTIR spectroscopy. The exposure of ampicillin in the absence (AM) and in the presence of the excipient (AMP) to UV light leads to an intensity diminution of the photoluminescence excitation (PLE) and photoluminescence (PL) spectra and the emergence of a new IR band at 3450 cm(-1). The photoluminescence studies demonstrate that the AM PD is amplified in the presence of excipients and an alkaline medium. In this last case, the PD process of AM involves the emergence of new compounds, whose presence is highlighted by: (i) the emergence of the isosbestic point at 300 nm in the UV-VIS spectra; (ii) a change in the ratio between the absorbance of IR bands situated in the spectral ranges 1200-1660 and 3250-3450 cm(-1); and (iii) a change in the ratio between the intensities of the Raman lines localized in the spectral ranges 1050-1800 and 2750-3100 cm(-1). A chemical mechanism of the PD processes of AM in an alkaline medium is proposed.

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.

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.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.

The effect of UV light on the cationic photopolymerization of the SU8 negative photoresist is shown by photoluminescence (PL) studies. Our results demonstrate that the cationic photopolymerization reaction of the SU8 photoresist takes place predominantly under the influence of the UVA light. Using UVA light, the influence of carbon nanotubes [of the types single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), multiwalled carbon nanotubes (MWNTs), and SWNTs functionalized with carboxyl groups (SWNTs-COOH)] on the cationic photopolymerization process of the SU8 photoresist is shown by PL studies. The cationic photopolymerization of the SU8 photoresist is monitored by the variations of the two emission bands with maxima at similar to 400-429 nm and 523-556 nm. The increase in the relative intensity of the PL band at similar to 523-556 nm is dependent on (i) the carbon nanotube concentration in the SU8 photoresist matrix; (ii) the type of carbon nanotubes, i.e., SWNTs, DWNTs, and MWNTs; and (iii) the nonfunctionalized and functionalized state of SWNTs. The results reported in this work demonstrate that PL can be used as a complementary method to Raman scattering and IR spectroscopy in the investigation of the cationic photopolymerization reaction of the SU8 negative photoresist. A decrease in the wrapping angle of carbon nanotubes with the SU8 photoresist is highlighted by anisotropic PL studies.

In this work, new optical properties of composites based on polystyrene (PS) microspheres and graphene oxide (GO) are reported. The radical polymerization of styrene in the presence of benzoyl peroxide, pentane and GO induces the appearance of new ester groups in the PS macromolecular chains remarked through an increase in the absorbance of the infrared (IR) band at 1743 cm(-1). The decrease in the GO concentration in the PS/GO composites mass from 5 wt.% to 0.5 wt.% induces a diminution in the intensities of the D and G Raman bands of GO simultaneous with a down-shift of the D band from 1351 to 1322 cm(-1). These variations correlated with the covalent functionalization of the GO layers with PS. For the first time, the photoluminescent (PL) properties of PS/GO composites are reported. The PS microspheres are characterized by a PL band at 397 nm. Through increasing the GO sheets' concentration in the PS/GO composite mass from 0.5 wt.% to 5 wt.%, a PS PL quenching process is reported. In addition, in the presence of ultraviolet A (UVA) light, a photo-degradation process of the PS/GO composite having the GO concentration equal to 5 wt.% is demonstrated by the PL studies.