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.

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.

The azathioprine (AZA) electrochemical adsorption onto the screen-printed carbon electrodes (SPCE) modified with the reduced graphene oxide (RGO) sheets in the absence and in the presence of polyaniline-emeraldine salt (PANI-ES) is reported in this work. Using cyclic voltammetry(CV), in the case of the SPCE modified with the RGO sheets non-functionalized and functionalized with PANI-ES, respectively, an irreversible process at the electrode/electrolyte interface is highlighted to take place. In the case of the SPCE modified with the non-functionalized RGO sheets(SPCE-RGO), the oxidation-reduction processes induce an up-shift of the AZA Raman lines from 856 and 1011 cm(-1) to 863 and 1020 cm(-1), respectively. These variations indicate an AZA adsorption onto the surface of the SPCE modified with the RGO sheets that takes place throughtthe imidazole and pyrimidine cycles of mercaptopurine, when the generation of the pi-pi(*) bonds between the mercaptopurine structure and hexagonal carbon cycles of RGO occurs. The electrochemical functionalization of the RGO sheets with PANI-ES is proved bythe appearance of the Raman lines at 1165, 1332-1371, 1496 and 1585 and 1616 cm(-1). The oxidation-reduction processes induced at the interface of the SPCE modified with PANI-ES functionalized RGO sheets and the electrolyte consisting into a phosphate buffer (PB) and AZA lead to thegeneration of new positive charges onto the PANI macromolecular chain and the adsorption of the drug on the working electrode surface that takes place via the pi-pi(*) bonds established between the benzene/quinoide rings of PANI and the imidazole/ purine cyclesof AZA. These results indicate that the SPCE modified with the PANI-ES functionalized RGO sheets shows potential applications in the field of sensors for AZA detection.

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.

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.

The influence of Ag and Au nanoparticles and reduced graphene oxide (RGO) sheets on the photodegradation of alpha-lipoic acid (ALA) was determined by UV-VIS spectroscopy. The ALA photodegradation was explained by considering the affinity of thiol groups for the metallic nanoparticles synthesized in the presence of trisodium citrate. The presence of excipients did not induce further changes when ALA interacts with Ag and Au nanoparticles with sizes of 5 and 10 nm by exposure to UV light. Compared to the Raman spectrum of ALA powder, changes in Raman lines' position and relative intensities when ALA has interacted with films obtained from Au nanoparticles with sizes between 5 and 50 nm were significant. These changes were explained by considering the chemical mechanism of surface-enhanced Raman scattering (SERS) spectroscopy. The photodegradation of ALA that had interacted with metallic nanoparticles was inhibited in the presence of RGO sheets.

The influence of Ag and Au nanoparticles and reduced graphene oxide (RGO) sheets on the photodegradation of alpha-lipoic acid (ALA) was determined by UV-VIS spectroscopy. The ALA photodegradation was explained by considering the affinity of thiol groups for the metallic nanoparticles synthesized in the presence of trisodium citrate. The presence of excipients did not induce further changes when ALA interacts with Ag and Au nanoparticles with sizes of 5 and 10 nm by exposure to UV light. Compared to the Raman spectrum of ALA powder, changes in Raman lines' position and relative intensities when ALA has interacted with films obtained from Au nanoparticles with sizes between 5 and 50 nm were significant. These changes were explained by considering the chemical mechanism of surface-enhanced Raman scattering (SERS) spectroscopy. The photodegradation of ALA that had interacted with metallic nanoparticles was inhibited in the presence of RGO sheets.

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.