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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. [ABSTRACT FROM AUTHOR]

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 A1g 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° to 39.9°. [ABSTRACT FROM AUTHOR]

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 ~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 ~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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Abstract In this work, the influence of silicotungstic acid concentration on the diphenylamine (DPA) electropolymerization in the absence and the presence of reduced graphene oxide (RGO) is studied. The optical properties of the composites based on polydiphenylamine (PDPA) doped with the H 4 SiW 12 O 40 heteropolyanions and RGO are investigated by Raman scattering, IR absorption spectroscopy and photoluminescence (PL). The presence of RGO induces an up-shift of the oxidation maximum of the DPA, as a result of a covalent functionalization process of graphene sheets with the polymer in the doped state. The deposition of PDPA onto RGO sheets surface is confirmed by the Raman scattering studies. Regardless of the H 4 SiW 12 O 40 concentration, an up-shift of the IR bands from 910 to 1014 cm−1 to ∼920 and 1022 cm−1 is reported as a consequence of the compensation of positive charges of PDPA macromolecular chains with of the H 4 SiW 12 O 40 heteropolyanions. An enhancement in the absorbance of the IR bands situated in the spectral range 750–1050 cm−1 accompanied of a decrease in the relative intensity of the PL bands of PDPA and their composites with RGO, as increasing the H 4 SiW 12 O 40 concentration, is reported. In the presence of RGO, a change in the PDPA PL spectra profile is also highlighted. Graphical abstract Image 1018328 Highlights • Electropolymerization of DPA in the presence of RGO and H 4 SiW 12 O 40 is studied. • Functionalization of RGO with PDPA is evidenced by the Raman and IR studies. • FTIR spectra proves insertion of the H 4 SiW 12 O 40 heteropolyanions in PDPA matrix. • A PDPA PL quenching process in the presence of RGO is highlighted. [ABSTRACT FROM AUTHOR]

A new composite material based on poly (para-phenylenevinylene) (PPV), pyrene (Py) and reduced graphene oxide (RGO) is synthesized using thermal conversion route. The properties of this material are investigated by Raman scattering, photoluminescence (PL), infrared (IR) and ultraviolet–visible (UV–Vis) spectroscopy. Adding Py at PPV precursor solution (PPV PS) containing RGO, yields to important modifications in both vibrational and electronic properties of these composites. The presence of Py into PPV matrix determines a blue shift of PPV PL. According to Raman and IR studies, PPV is non-covalently functionalized with Py which interacts forward with RGO through π-π interactions causing an important modification into the polymer chains conjugation length. [ABSTRACT FROM AUTHOR]

Significant differences are reported for the IR spectra of poly[(2,5-bisoctyloy)-1, 4-phenylenevinylene] (BO-PPV) recorded onto the KBr, Ag and Au supports. In this work, a decrease in the absorbance of the IR spectra of the BO-PPV films deposited onto Au and Ag supports as increasing the macromolecular compound film thickness is reported. A preferential orientation of the BO-PPV molecules and its composite with single-walled carbon nanotubes (SWNTs) versus metallic supports of Ag and Au is assessed using the IR absorption spectroscopy under s and p polarized light. An anti-Stokes photoluminescence (ASPL) is reported to characterize the BO-PPV macromolecular compound. The BO-PPV ASPL spectra intensity dependent both of the thickness of the macromolecular compound layer deposited onto the metallic supports and the SWNTs weight in the BO-PPV/SWNTs composite mass. [ABSTRACT FROM AUTHOR]

We report new photoluminescence (PL) data generated by pulsed optical excitation on the composites achieved by a mechanico-chemical reaction between ZnS in the cubic (c) and wurtzite (w) phases and polyaniline-emeraldine base (PANI-EB). Under continuous and pulsed optical excitation, powders of the (w)ZnS and (w)ZnS/PANI-EB composites display PL with different spectral compositions. Contrary to expectations, the (c)ZnS and the (c)ZnS/PANI-EB composite displayed weak PL and decay time in the range of nanoseconds. This results from the great involvement of the surface states in nanometric powders which creates efficient channels for the non-radiative recombination of the carriers. [ABSTRACT FROM AUTHOR]

Abstract: Polydiphenylamine/single walled carbon nanotube (PDPA/SWNT) composites were synthesized electrochemically aiming at their application as active electrode materials for rechargeable lithium batteries. The electrochemical polymerization of diphenylamine (DPA) on a SWNT film immersed in a 1M HCl solution was studied by cyclic voltammetry. Comparing cyclic voltammograms recorded on a blank Pt electrode with those obtained for a SWNT film deposited on Pt electrode one observes in the latter case a decrease of the DPA reduction potential. To elucidate electrochemical polymerization mechanism, photoluminescence studies on DPA/SWNT and PDPA/SWNT systems were carried out. Additional information concerning the functionalization process of SWNT with PDPA was obtained by Raman and IR spectroscopy. Using the PDPA/SWNT composite as active material for the positive electrode of a rechargeable lithium cell (LiPF6 electrolyte), the charge–discharge tests show a specific discharge capacity of ca. 245mAhg−1, much higher than the 35mAhg−1 for pure PDPA. [ABSTRACT FROM AUTHOR]

This paper prepared composites under the free membranes form that are based on thermoplastic polymers of the type of polyurethane (TPU) and polyolefin (TPO), which are blended in the weight ratio of 2:1, and ceramic nanoparticles (CNs) such as BaSrTiO3 and SrTiO3. The structural, optical, and conductive properties of these new composite materials are reported. The X-ray diffraction studies highlight a cubic crystalline structure of these CNs. The main variations in the vibrational properties of the TPU:TPO blend induced by CNs consist of the following: (i) the increase in the intensity of the Raman line of 1616 cm−1; (ii) the down-shift of the IR band from 800 to 791 cm−1; (iii) the change of the ratio between the absorbance of IR bands localized in the spectral range 950–1200 cm−1; and (iv) the decrease in the absorbance of the IR band from 1221 cm−1. All these variations were correlated with a preferential adsorption of thermoplastic polymers on the CNs surface. A photoluminescence (PL) quenching process of thermoplastic polymers is demonstrated to occur in the presence of CNs. The anisotropic PL measurements have highlighted a change in the angle of the binding of the TPU:TPO blend, which varies from 23.7° to ≈49.3° and ≈53.4°, when the concentration of BaSrTiO3 and SrTiO3 CNs, respectively, is changed from 0 to 25 wt. %. Using dielectric spectroscopy, two mechanisms are invoked to take place in the case of the composites based on TPU:TPO blends and CNs, i.e., one regarding the type of the electrical conduction and another specifying the dielectric–dipolar relaxation processes. [ABSTRACT FROM AUTHOR]

In this work, synthesis and optical properties of a new composite based on poly(o-phenylenediamine) (POPD) fiber like structures, poly(vinylidene fluoride) (PVDF) spheres and double-walled carbon nanotubes (DWNTs) are reported. As increasing the PVDF weight in the mixture of the chemical polymerization reaction of o-phenylenediamine, the presence of the PVDF spheres onto the POPD fibers surface is highlighted by scanning electron microscopy (SEM). The down-shift of the Raman line from 1421 cm−1 to 1415 cm−1 proves the covalent functionalization of DWNTs with the POPD-PVDF blends. The changes in the absorbance of the IR bands peaked around 840, 881, 1240 and 1402 cm−1 indicate hindrance steric effects induced of DWNTs to the POPD fiber like structures and the PVDF spheres, as a consequence of the functionalization process of carbon nanotubes with macromolecular compounds. The presence of the PVDF spheres onto the POPD fiber like structures surface induces a POPD photoluminescence (PL) quenching process. An additional PL quenching process of the POPD-PVDF blends is reported to be induced in the presence of DWNTs. The studies of anisotropic PL highlight a change of the angle of the binding of the PVDF spheres onto the POPD fiber like structures surface from 50.2° to 38° when the carbon nanotubes concentration increases in the POPD-PVDF/DWNTs composites mass up to 2 wt.%. [ABSTRACT FROM AUTHOR]

Photodegradation of the aqueous solutions of acetylsalicylic acid, in the absence (ASA) and the presence of excipients (ASE), is demonstrated by the photoluminescence (PL). A shift of the PL bands from 342 and 338 nm to 358 and 361–397 nm for ASA and ASE in solid state and as aqueous solutions was reported. By exposure of the solution of ASA 0.3 M to UV light, a decrease in the PL band intensity was highlighted. This behavior was revealed for ASA in the presence of phosphate buffer (PB) having the pH equal to 6.4, 7, and 8 or by the interaction with NaOH 0.3 M. A different behavior was reported in the case of ASE. In the presence of PB, an increase in the intensity of the PL band of ASE simultaneously with a change of the ratio between the intensities of the bands at 361–364 and 394–397 nm was highlighted. The differences between PL spectra of ASA and ASE have their origin in the presence of salicylic acid (SAL). The interaction of ASE with NaOH induces a shift of the PL band at 405–407 nm. Arguments for the reaction of ASA with NaOH are shown by Raman scattering and FTIR spectroscopy. [ABSTRACT FROM AUTHOR]

In this work, the effect of the single-walled carbon nanotubes (SWNTs) as the mixtures of metallic and semiconducting tubes (M + S-SWNTs) as well as highly separated semiconducting (S-SWNTs) and metallic (M-SWNTs) tubes on the photoluminescence (PL) of poly(3-hexyl thiophene) (P3HT) was reported. Two methods were used to prepare such composites, that is, the chemical interaction of the two constituents and the electrochemical polymerization of the 3-hexyl thiophene onto the rough Au supports modified with carbon nanotubes (CNTs). The measurements of the anisotropic PL of these composites have highlighted a significant diminution of the angle of the binding of the P3HT films electrochemical synthetized onto Au electrodes covered with M + S-SWNTs. This change was attributed to metallic tubes, as was demonstrated using the anisotropic PL measurements carried out on the P3HT/M-SWNTs and P3HT/S-SWNTs composites. Small variations in the angle of the binding were reported in the case of the composites prepared by chemical interaction of the two constituents. The proposed mechanism to explain this behavior took into account the functionalization process of CNTs with P3HT. The experimental arguments of the functionalization process of CNTs with P3HT were shown by the UV-VIS-NIR and FTIR spectroscopy as well as surface-enhanced Raman scattering (SERS). A PL quenching process of P3HT induced both in the presence of S-SWNTs and M-SWNTs was reported, too. This process origins in the various de-excitation pathways which can be developed considering the energy levels diagram of the two constituents of each studied composite. [ABSTRACT FROM AUTHOR]

In this work, new evidence for the photodegradation reactions of acetaminophen (AC) is reported by photoluminescence (PL), Raman scattering and FTIR spectroscopy. Under excitation wavelength of 320 nm, AC shows a PL band in the spectral range of 340–550 nm, whose intensity decreases by exposure to UV light. The chemical interaction of AC with the NaOH solutions, having the concentration ranging between 0.001 and 0.3 M, induces a gradual enhancement of the photoluminescence excitation (PLE) and PL spectra, when the exposure time of samples at the UV light increases until 140 min, as a result of the formation of p-aminophenol and sodium acetate. This behavior is not influenced by the excipients or other active compounds in pharmaceutical products as demonstrated by PLE and PL studies. Experimental arguments for the obtaining of p-aminophenol and sodium acetate, when AC has interacted with NaOH, are shown by Raman scattering and FTIR spectroscopy. [ABSTRACT FROM AUTHOR]

In this work, a complementary ultraviolet-visible (UV-VIS) spectroscopy and photoluminescence (PL) study on melatonin (MEL) hydrolysis in the presence of alkaline aqueous solutions and the photodegradation of MEL is reported. The UV-VIS spectrum of MEL is characterized by an absorption band with a peak at 278 nm. This peak shifts to 272 nm simultaneously with an increase in the band absorbance at 329 nm in the presence of an NaOH solution. The isosbestic point localized at 308 nm indicates the generation of some chemical compounds in addition to MEL and NaOH. The MEL PL spectrum is characterized by a band at 365 nm. There is a gradual decrease in the MEL PL intensity as the alkaline solution concentration added at the drug solution is increased. In the case of the MEL samples interacting with an alkaline solution, a new photoluminescence excitation (PLE) band at 335 nm appears when the exposure time to UV light reaches 310 min. A down-shift in the MEL PLE band, from 321 to 311 nm, as a consequence of the presence of excipients, is also shown. These changes are explained in reference to the MEL hydrolytic products. [ABSTRACT FROM AUTHOR]

In this work, we report a photodegradation process of azathioprine (AZA) highlighted by correlated studies of photoluminescence (PL) and the UV-VIS and IR absorption spectroscopy. The photodegradation process of AZA is observed by the gradual increasing in the intensity of the PL spectrum recorded under the excitation wavelength of 300 nm. This behaviour is accompanied, in the photoluminescence excitation (PLE) spectra, by a gradual intensity decreasing of the PLE band situated in the 250–320 nm spectral range simultaneous with the intensity increasing of the PLE band localized in the 325–425 nm spectral range. Regardless if the immunosuppressive compound is in the state of powder, tablet or solution, the PL and UV-VIS absorption spectroscopy studies have demonstrated that a photodegradation process under UV light takes place. According to the PL studies carried out in ambient and vacuum condition, the photodegradation process of AZA was demonstrated to be influenced by the oxygen from air. The presence of a new IR band with maximum at 1745 cm−1 confirms the AZA photodegradation pathway proposed in this work. [ABSTRACT FROM AUTHOR]