{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,23]],"date-time":"2026-08-23T15:52:57Z","timestamp":1787500377533,"version":"build-2736575974"},"reference-count":41,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2022,4,2]],"date-time":"2022-04-02T00:00:00Z","timestamp":1648857600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"European Regional Development Fund under the Competitiveness Operational Program 2014-2020","award":["POC 58\/2016"],"award-info":[{"award-number":["POC 58\/2016"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>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\u2013400 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\u2013335 and 335\u2013430 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\u22121 to 1331 cm\u22121, 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\u22121 and 1330 cm\u22121 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.<\/jats:p>","DOI":"10.3390\/ijms23073975","type":"journal-article","created":{"date-parts":[[2022,4,3]],"date-time":"2022-04-03T02:59:52Z","timestamp":1648954792000},"page":"3975","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Photodegradation of Azathioprine in the Presence of Sodium Thiosulfate"],"prefix":"10.3390","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3828-9159","authenticated-orcid":false,"given":"N\u2019ghaya","family":"Toulbe","sequence":"first","affiliation":[{"name":"Laboratory of Optical Processes in Nanostructured Materials, National Institute of Materials Physics, Atomistilor Street 405A, MG-7, 077125 Bucharest, Romania"},{"name":"Interdisciplinary School of Doctoral Studies, University of Bucharest, \u0218oseaua Panduri 90, 050663 Bucharest, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ion","family":"Smaranda","sequence":"additional","affiliation":[{"name":"Laboratory of Optical Processes in Nanostructured Materials, National Institute of Materials Physics, Atomistilor Street 405A, MG-7, 077125 Bucharest, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Catalin","family":"Negrila","sequence":"additional","affiliation":[{"name":"Nanoscale Condensed Matter Laboratory, National Institute of Materials Physics, Atomistilor Street 405A, MG-7, 077125 Bucharest, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3916-5112","authenticated-orcid":false,"given":"Cristina","family":"Bartha","sequence":"additional","affiliation":[{"name":"Laboratory of Magnetism & Superconductivity, National Institute of Materials Physics, Atomistilor Street 405A, MG-7, 077125 Bucharest, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3506-6945","authenticated-orcid":false,"given":"Corina M.","family":"Manta","sequence":"additional","affiliation":[{"name":"SARA Pharm Solutions S.R.L., 266-268 Calea Rahovei, 050912 Bucharest, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mihaela","family":"Baibarac","sequence":"additional","affiliation":[{"name":"Laboratory of Optical Processes in Nanostructured Materials, National Institute of Materials Physics, Atomistilor Street 405A, MG-7, 077125 Bucharest, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,4,2]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"258","DOI":"10.4103\/0971-4065.85483","article-title":"Comparison of azathioprine with mycophenolate mofetil in a living donor kidney transplant programme","volume":"21","author":"Bansal","year":"2011","journal-title":"Indian J. Nephrol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"18","DOI":"10.1136\/ard.41.Suppl_1.18","article-title":"Long-term effects of azathioprine in rheumatoid arthritis","volume":"41","author":"Urowitz","year":"1982","journal-title":"Ann. Rheum. Dis."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"527","DOI":"10.1016\/S0190-9622(87)70069-3","article-title":"Azathioprine in the treatment of pemphigus vulgaris: A long-term follow-up","volume":"16","author":"Aberer","year":"1987","journal-title":"J. Am. Acad. Dermatol."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"141","DOI":"10.1080\/09629359891045","article-title":"Azathioprine in inflammatory bowel disease, a safe alternative?","volume":"7","author":"Tanis","year":"1998","journal-title":"Mediat. Inflamm."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1691","DOI":"10.1007\/s00296-014-3026-y","article-title":"Systemic sclerosis: Comparison of efficacy of oral cyclophosphamide and azathioprine on skin score and pulmonary involvement\u2014A retrospective study","volume":"34","author":"Poormoghim","year":"2014","journal-title":"Rheumatol. Int."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1517\/14622416.3.1.89","article-title":"The thiopurine S-methyltansferase gene locus\u2014Implications for clinical pharmacogenomics","volume":"3","author":"McLeod","year":"2002","journal-title":"Pharmacogenomics"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"138","DOI":"10.1111\/j.1365-2613.2008.00575.x","article-title":"The haemotoxicity of azathioprine in repeat dose studies in the female CD-1 mouse","volume":"89","author":"Molyneux","year":"2008","journal-title":"Int. J. Exp. Pathol."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"3621","DOI":"10.1016\/j.electacta.2010.01.099","article-title":"Glassy carbon electrodes modified with a film of nanodiamond-graphite\/chitosan: Application to the highly sensitive electrochemical determination of Azathioprine","volume":"55","author":"Shahrokhian","year":"2010","journal-title":"Electrochim. Acta"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"287","DOI":"10.1016\/0378-4347(95)00365-7","article-title":"High-performance liquid chromatographic assay for the measurement of azathioprine in human serum samples","volume":"675","author":"Binscheck","year":"1996","journal-title":"J. Chromatogr. B Biomed. Appl."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"239","DOI":"10.1002\/jccs.201100369","article-title":"Direct determination of azathioprine in human fluids and pharmaceutical formulation using flow injection chemiluminescence analysis","volume":"59","author":"Wang","year":"2012","journal-title":"J. Chinese Chem. Soc."},{"key":"ref_11","first-page":"235","article-title":"Quantitative determination of Azathioprine in tablets by1H NMR spectroscopy","volume":"53","author":"Parlatan","year":"1998","journal-title":"J. Pharm. Belg."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"702","DOI":"10.1016\/j.molstruc.2018.10.065","article-title":"Novel anhydrous solid-state form of Azathioprine: The assessing of crystal structure by powder X-Ray diffraction, Infrared Absorption Spectroscopy and Raman scattering","volume":"1178","author":"Covaci","year":"2019","journal-title":"J. Mol. Struct."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"8084","DOI":"10.1021\/acs.jpcc.7b01179","article-title":"Electrochemical-Surface Enhanced Raman Spectroscopic (EC-SERS) Study of 6-Thiouric Acid: A Metabolite of the Chemotherapy Drug Azathioprine","volume":"121","author":"Greene","year":"2017","journal-title":"J. Phys. Chem. C"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"102443","DOI":"10.1016\/j.rinp.2019.102443","article-title":"The influence of UV light on the azathioprine photodegradation: New evidences by photoluminescence","volume":"14","author":"Smaranda","year":"2019","journal-title":"Results Phys."},{"key":"ref_15","first-page":"1572526","article-title":"A new electrochemical sensor for direct detection of purine antimetabolites and DNA degradation","volume":"2019","author":"Shpigun","year":"2019","journal-title":"J. Anal. Methods Chem. D"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1098","DOI":"10.1016\/j.msec.2015.09.022","article-title":"Voltammetric studies of Azathioprine on the surface of graphite electrode modified with graphene nanosheets decorated with Ag nanoparticles","volume":"58","author":"Asadian","year":"2016","journal-title":"J. Mater. Sci. Eng. C"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"7446","DOI":"10.20964\/2017.08.145","article-title":"Determination of Non-Steroidal Anti-Inflammatory Drug (NSAID) azathioprine in human blood serum and tablet samples using Multi-Walled Carbon Nanotubes (MWCNTs) decorated manganese oxide microcubes composite film modified electrode","volume":"12","author":"Muthumariappan","year":"2017","journal-title":"Int. J. Electrochem. Sci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"458","DOI":"10.1016\/0190-9622(95)90069-1","article-title":"Skin cancer in heart transplant recipients","volume":"32","author":"Redondo","year":"1995","journal-title":"J. Am. Acad. Dermatol."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"526","DOI":"10.1016\/j.cej.2016.05.085","article-title":"Kinetic and mechanistic investigation of azathioprine degradation in water by UV, UV\/H2O2 and UV\/persulfate","volume":"302","author":"Zhang","year":"2016","journal-title":"Chem. Eng. J."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"566","DOI":"10.1103\/PhysRevLett.45.566","article-title":"Ground State of the Electron Gas by a Stochastic Method","volume":"45","author":"Ceperley","year":"1980","journal-title":"Phys. Rev. Lett."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1038\/nrc2292","article-title":"Thiopurines in current medical practice: Molecular mechanisms and contributions to therapy-related cancer","volume":"8","author":"Karran","year":"2008","journal-title":"Nat. Rev. Cancer"},{"key":"ref_22","doi-asserted-by":"crossref","unstructured":"Barbatu, A., Lungan, M.A., Toulbe, N., Smaranda, I., Daescu, M., Baibarac, M., and Manta, C.M. (2022). Physico-chemical properties of two anhydrous azathioprine forms and their interaction with typical pharmaceutical excipients: Highlighting new findings in drug formulation development. Drug Dev. Ind. Pharm.","DOI":"10.1080\/03639045.2022.2032131"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"50","DOI":"10.31788\/RJC.2019.1214073","article-title":"Green synthesis of sulphur nanoparticles using Aqueous garlic extract (Allium sativum)","volume":"12","author":"Khairan","year":"2019","journal-title":"Rasayan J. Chem."},{"key":"ref_24","unstructured":"Silverstein, R.M., Bassler, G.C., and Morrill, T.C. (1991). Spectrometric Identification of Organic Compounds, John Wiley & Sons. [4th ed.]."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"107643","DOI":"10.1016\/j.compbiolchem.2022.107643","article-title":"Synthesis, structural elucidation, DFT calculation, biological studies and DNA interaction of some aryl hydrazone Cr3+, Fe3+, and Cu2+ chelates","volume":"97","author":"Aljohani","year":"2022","journal-title":"Comput. Biol. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"130693","DOI":"10.1016\/j.molstruc.2021.130693","article-title":"Synthesis and intensive characterization for novel Zn(II), Pd(II), Cr(III) and VO(II)-Schiff base complexes; DNA-interaction, DFT, drug-likeness and molecular docking studies","volume":"1242","author":"Aljohani","year":"2021","journal-title":"J. Mol. Struct."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"S1835","DOI":"10.1016\/j.arabjc.2013.07.010","article-title":"DNA binding ability mode, spectroscopic studies, hydrophobicity, and in vitro antibacterial evaluation of some new Fe(II) complexes bearing ONO donors amino acid Schiff bases","volume":"10","author":"Nassr","year":"2017","journal-title":"Arab. J. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"272","DOI":"10.1002\/jrs.1250160410","article-title":"Raman spectra of copper(I), silver(I) and gold(I) cyanides in aqueous solutions of sodium thiosulphate","volume":"16","author":"Peter","year":"1985","journal-title":"J. Raman Spectrosc."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"394","DOI":"10.1016\/j.saa.2013.05.041","article-title":"Tautomerism and spectroscopic properties of the immunosuppressant azathioprine","volume":"114","author":"Makhyoun","year":"2013","journal-title":"Spectrochim. Acta"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"866","DOI":"10.1002\/jrs.750","article-title":"Assignment of the Raman-active modes of the antitumor agent azathioprine by normal-mode calculations","volume":"32","author":"Vivoni","year":"2001","journal-title":"J. Raman Spectrosc."},{"key":"ref_31","first-page":"286","article-title":"Molecular spectroscopy by means of ESCA","volume":"1","author":"Lindberg","year":"1970","journal-title":"Phys. Scr."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"945","DOI":"10.1039\/b814729a","article-title":"Sputter-induced chemical transformation in oxoanions by combination of C60+ and Ar+ ion beams analyzed with X-ray photoelectron spectrometry","volume":"134","author":"Lin","year":"2009","journal-title":"Analyst"},{"key":"ref_33","unstructured":"Moulder, J.F. (1995). Handbook of X-ray Photoelectron Spectroscopy, Physical Electronics."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"114809","DOI":"10.1016\/j.molliq.2020.114809","article-title":"Purine derivatives as high efficient eco-friendly inhibitors for the corrosion of mild steel in acidic medium: Experimental and theoretical calculations","volume":"323","author":"Jiang","year":"2021","journal-title":"J. Mol. Liq."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1016\/j.jcis.2020.03.065","article-title":"Inhibitive and adsorption behavior of thiadiazole derivatives on carbon steel corrosion in CO2-saturatd oilfield produced water:effect of substituent group on efficiency","volume":"572","author":"Zhang","year":"2020","journal-title":"J. Colloid Interface Sci."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"567","DOI":"10.1016\/S1381-1169(00)00147-3","article-title":"Thiol protected platinum black and palladium black catalysts in oxidation catalysis","volume":"158","author":"Berezin","year":"2000","journal-title":"J. Mol. Catal. A Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"151","DOI":"10.3389\/fchem.2019.00151","article-title":"Core shell investigation of 2-nitroimidazole","volume":"7","author":"Bolognesi","year":"2019","journal-title":"Front. Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"541","DOI":"10.1023\/A:1013125203444","article-title":"Thermal analysis of hydrated silica-sodium thiosulfate-sulfur system","volume":"66","author":"Teodorczyk","year":"2001","journal-title":"J. Therm. Anal. Calorim."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2013","DOI":"10.1080\/10643389.2012.672047","article-title":"The Importance of Thiosalts Speciation, Review of Analytical Methods, Kinetics, and Treatment","volume":"43","author":"Pappoe","year":"2013","journal-title":"Crit. Rev. Environ. Sci. Technol."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Watson, J.T., and Sparkman, O.D. (2007). Introduction to Mass Spectrometry: Instrumentation, Applications and Strategies for Data Interpretation, John Wiley&Sons Ltd.. [4th ed.].","DOI":"10.1002\/9780470516898"},{"key":"ref_41","unstructured":"William, E. (2022, January 18). Wallace, Mass Spectra by NIST Mass Spectrometry Data Center in NIST Chemistry Web Book SRD 69, Available online: http:\/\/webbook.nist.gov."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/7\/3975\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T22:49:08Z","timestamp":1760136548000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/7\/3975"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,4,2]]},"references-count":41,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2022,4]]}},"alternative-id":["ijms23073975"],"URL":"https:\/\/doi.org\/10.3390\/ijms23073975","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,4,2]]}}}