{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,29]],"date-time":"2025-10-29T06:28:40Z","timestamp":1761719320853,"version":"build-2065373602"},"reference-count":41,"publisher":"MDPI AG","issue":"22","license":[{"start":{"date-parts":[[2024,11,20]],"date-time":"2024-11-20T00:00:00Z","timestamp":1732060800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Institute of Physics, Polish Academy of Sciences","award":["UIDB\/EQU\/00102\/2020","UIDP\/EQU\/00102\/2020"],"award-info":[{"award-number":["UIDB\/EQU\/00102\/2020","UIDP\/EQU\/00102\/2020"]}]},{"name":"Portuguese Science Foundation","award":["UIDB\/EQU\/00102\/2020","UIDP\/EQU\/00102\/2020"],"award-info":[{"award-number":["UIDB\/EQU\/00102\/2020","UIDP\/EQU\/00102\/2020"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Monomers of N-hydroxypyridine-2(1H)-thione were isolated in low-temperature matrices of solid normal hydrogen (n-H2). The matrix-isolated compound was irradiated with UV-B (\u03bb = 305 nm) or UV-A (\u03bb &gt; 360 nm) light. Upon such irradiation, the initial form of N-hydroxypyridine-2(1H)-thione was completely consumed and converted into photoproducts. 2-Mercaptopyridine and water were identified as the main products of these photochemical transformations. Identification of photoproduced 2-mercaptopyridine is unquestionable. It is based on the identity of two sets of IR bands: (i) the bands observed in the IR spectrum recorded (in a separate experiment) for monomers of 2-mercaptopyridine trapped in an n-H2 matrix and (ii) a set of IR bands observed in the spectrum recorded after UV irradiation of N-hydroxypyridine-2(1H)-thione. It should be emphasized that the UV-induced processes, occurring for N-hydroxypyridine-2(1H)-thione isolated in an n-H2 matrix, lead to products that are significantly different from those generated from the compound trapped in solid Ar or in solid N2.<\/jats:p>","DOI":"10.3390\/molecules29225472","type":"journal-article","created":{"date-parts":[[2024,11,20]],"date-time":"2024-11-20T07:02:58Z","timestamp":1732086178000},"page":"5472","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Photochemical Hydroxyl Group Abstraction from N-Hydroxypyridine-2(1H)-thione Isolated in a Solid Hydrogen Matrix: Photogeneration of 2-Mercaptopyridine"],"prefix":"10.3390","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9186-0705","authenticated-orcid":false,"given":"Hanna","family":"Rostkowska","sequence":"first","affiliation":[{"name":"Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32\/46, 02-668 Warsaw, Poland"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0693-4109","authenticated-orcid":false,"given":"Maciej J.","family":"Nowak","sequence":"additional","affiliation":[{"name":"Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32\/46, 02-668 Warsaw, Poland"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5983-7743","authenticated-orcid":false,"given":"Igor","family":"Reva","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering, CERES, University of Coimbra, 3030-790 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2896-4007","authenticated-orcid":false,"given":"Leszek","family":"Lapinski","sequence":"additional","affiliation":[{"name":"Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32\/46, 02-668 Warsaw, Poland"}]}],"member":"1968","published-online":{"date-parts":[[2024,11,20]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Jones, B.A., and Katritzky, A.R. (1960). N-Oxides and Related Compounds. Part XVII. The Tautomerism of Mercapto- and Acylamino-pyridine 1-Oxides. J. Chem. Soc., 2937\u20132942.","DOI":"10.1039\/jr9600002937"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"105","DOI":"10.1007\/s00214-016-1870-4","article-title":"Electronic Excitation and Ionization Behavior of N-Hydroxypyridine-2(1H)-thione and its Deprotonated Anion in a Polarizable Medium Studied Using Quantum Chemical Computations","volume":"135","author":"Fukuda","year":"2016","journal-title":"Theor. Chem. Acc."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"238","DOI":"10.1021\/jp077365r","article-title":"Thioperoxy Derivative Generated by UV-Induced Transformation of N-Hydroxypyridine-2(1H)-thione Isolated in Low-Temperature Matrixes","volume":"112","author":"Lapinski","year":"2008","journal-title":"J. Phys. Chem. A"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1536","DOI":"10.1107\/S0108270199006824","article-title":"1-Hydroxy-2(1H)-pyridinethione","volume":"55","author":"Bond","year":"1999","journal-title":"Acta Crystallogr. C."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"10113","DOI":"10.1021\/ja961988t","article-title":"Photochemistry of the Nonspecific Hydroxyl Radical Generator, N-Hydroxypyridine-2(1H)-thione","volume":"118","author":"Aveline","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"ref_6","unstructured":"Larionov, O.V. (2017). Chapter 5. Recent Advances in the Photochemistry of Heterocyclic N-Oxides and Their Derivatives. Heterocyclic N-Oxides, Springer International Publishing."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1625","DOI":"10.1093\/nar\/24.9.1625","article-title":"Photolysis of N-Hydroxypyridinethiones: A New Source of Hydroxyl Radicals for the Direct Damage of Cell-Free and Cellular DNA","volume":"24","author":"Epe","year":"1996","journal-title":"Nucleic Acids Res."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"77","DOI":"10.1016\/S0378-4274(02)00279-5","article-title":"Studies on Cytotoxic and Genotoxic Effects of N-Hydroxypyridine-2-thione (Omadine) in L5178Y Mouse Lymphoma Cells","volume":"136","author":"Adam","year":"2002","journal-title":"Toxicol. Lett."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"7154","DOI":"10.1021\/jp3033337","article-title":"Hydroxyl Radical Reaction with trans-Resveratrol: Initial Carbon Radical Adduct Formation Followed by Rearrangement to Phenoxyl Radical","volume":"116","author":"Li","year":"2012","journal-title":"J. Phys. Chem. B"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2082","DOI":"10.1021\/jp1100889","article-title":"Direct Observation of the \u03b2-Carotene Reaction with Hydroxyl Radical","volume":"115","author":"Chen","year":"2011","journal-title":"J. Phys. Chem. B"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Halliwell, B., and Gutteridge, J.M.C. (2015). Free Radicals in Biology and Medicine, Oxford Academic. [5th ed.].","DOI":"10.1093\/acprof:oso\/9780198717478.001.0001"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"8355","DOI":"10.1039\/D1CS00044F","article-title":"Hydroxyl Radical is a Significant Player in Oxidative DNA Damage in vivo","volume":"50","author":"Halliwell","year":"2021","journal-title":"Chem. Soc. Rev."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1468","DOI":"10.1242\/jcs.064352","article-title":"Arabidopsis Root K+-Efflux Conductance Activated by Hydroxyl Radicals: Single-Channel Properties, Genetic Basis and Involvement in Stress-Induced Cell Death","volume":"123","author":"Demidchik","year":"2010","journal-title":"J. Cell Sci."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"81","DOI":"10.1242\/jcs.00201","article-title":"Free Oxygen Radicals Regulate Plasma Membrane Ca2+ and K+ Permeable Channels in Plant Root Cells","volume":"116","author":"Demidchik","year":"2003","journal-title":"J. Cell Sci."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"103027","DOI":"10.1016\/j.dnarep.2020.103027","article-title":"Towards a Comprehensive View of 8-Oxo-7,8-dihydro-2\u2032-deoxyguanosine: Highlighting the Intertwined Roles of DNA Damage and Epigenetics in Genomic Instability","volume":"97","author":"Gorini","year":"2021","journal-title":"DNA Repair"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/j.mrfmmm.2004.09.012","article-title":"Ultraviolet Radiation-Mediated Damage to Cellular DNA","volume":"571","author":"Cadet","year":"2005","journal-title":"Mutat. Res."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1016\/j.mrfmmm.2003.09.001","article-title":"Oxidative Damage to DNA: Formation, Measurement and Biochemical Features","volume":"531","author":"Cadet","year":"2003","journal-title":"Mutat. Res."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"10448","DOI":"10.1021\/bi0009136","article-title":"Studies of RNA Cleavage by Photolysis of N-Hydroxypyridine-2(1H)-thione. A New Photochemical Footprinting Method","volume":"39","author":"Chaulk","year":"2000","journal-title":"Biochemistry"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"9699","DOI":"10.1021\/ja00143a013","article-title":"Photochemistry of N-Hydroxypyridine-2-thione Derivatives: Involvement of the 2-Pyridylthiyl Radical in the Radical Chain Reaction Mechanism","volume":"117","author":"Aveline","year":"1995","journal-title":"J. Am. Chem. Soc."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"289","DOI":"10.1021\/ja953293i","article-title":"N-Hydroxypyridine-2(1H)-thione: Not a Selective Generator of Hydroxyl Radicals in Aqueous Solution","volume":"118","author":"Aveline","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"van Kranendonk, J. (1983). Chapter 5. Lattice Vibrations and Elastic Properties. Solid Hydrogen: Theory of the Properties of Solid H2, HD and D2, Springer. [1st ed.]. Available online: https:\/\/link.springer.com\/chapter\/10.1007\/978-1-4684-4301-1_5.","DOI":"10.1007\/978-1-4684-4301-1"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"094306","DOI":"10.1063\/1.4977604","article-title":"Solid H2 versus Solid Noble-gas Environment: Influence on Photoinduced Hydrogen-Atom Transfer in Matrix-Isolated 4(3H)-Pyrimidinone","volume":"146","author":"Lapinski","year":"2017","journal-title":"J. Chem. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"7437","DOI":"10.1021\/acs.jpca.1c05538","article-title":"Effect of a Solid hydrogen Environment on UV-Induced Hydrogen-Atom Transfer in Matrix-Isolated Heterocyclic Thione Compounds","volume":"125","author":"Rostkowska","year":"2021","journal-title":"J. Phys. Chem. A"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"11447","DOI":"10.1039\/C7CP01363A","article-title":"UV-induced Hydrogen-Atom Transfer and Hydrogen-Atom Detachment in Monomeric 7-Azaindole Isolated in Ar and n-H2 Matrices","volume":"19","author":"Nowak","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"21589","DOI":"10.1039\/D4CP02400A","article-title":"Hydrogen-Atom-Assisted Processes on Thioacetamide in para-H2 matrix\u2014Formation of Thiol Tautomers","volume":"26","author":"Keresztes","year":"2024","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"14526","DOI":"10.1021\/jp2080385","article-title":"Microwave Spectra and Gas Phase Structural Parameters for N-Hydroxypyridine-2(1H)-thione","volume":"115","author":"Daly","year":"2011","journal-title":"J. Phys. Chem. A"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"7406","DOI":"10.1021\/j100382a018","article-title":"Theoretical and Matrix-Isolation Experimental Study on 2(1H)-Pyridinethione\/2-Pyridinethiol","volume":"94","author":"Nowak","year":"1990","journal-title":"J. Phys. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"12142","DOI":"10.1021\/jp2059563","article-title":"UV-Induced Hydrogen-Atom Transfer in 3,6-Dithiopyridazine and in Model Compounds 2-Thiopyridine and 3-Thiopyridazine","volume":"115","author":"Rostkowska","year":"2011","journal-title":"J. Phys. Chem. A"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"17622","DOI":"10.1002\/anie.202006640","article-title":"Heavy-Atom Tunneling Through Crossing Potential Energy Surfaces: Cyclization of a Triplet 2-Formylarylnitrene to a Singlet 2,1-Benzisoxazole","volume":"59","author":"Nunes","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"34","DOI":"10.1016\/j.molstruc.2017.11.009","article-title":"Photochemistry of Matrix-Isolated 3-Chloro-1,2-benzisoxazole: Generation and Characterization of 2-Cyanophenoxyl Radical and Other Reactive Intermediates","volume":"1172","author":"Nunes","year":"2018","journal-title":"J. Molec. Struct."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"16169","DOI":"10.1039\/C7CP02621H","article-title":"Reaction of H + HONO in Solid para-Hydrogen: Infrared Spectrum of \u2022ONH(OH)","volume":"19","author":"Haupa","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1481","DOI":"10.1021\/cr9404609","article-title":"Molecular Photodynamics in Rare Gas Solids","volume":"99","author":"Apkarian","year":"1999","journal-title":"Chem. Rev."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"2200","DOI":"10.1039\/c3cp54184c","article-title":"Infrared Spectra of Free Radicals and Protonated Species Produced in para-Hydrogen Matrices","volume":"16","author":"Bahou","year":"2014","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"393","DOI":"10.1103\/RevModPhys.52.393","article-title":"The Solid Molecular Hydrogens in the Condensed Phase: Fundamentals and Static Properties","volume":"52","author":"Silvera","year":"1980","journal-title":"Rev. Mod. Phys."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"3706","DOI":"10.1063\/1.1642582","article-title":"Tunneling Chemical Reactions in Solid Parahydrogen: Direct Measurement of the Rate Constants of R+H2\u2192RH+H (R=CD3, CD2H, CDH2, CH3) at 5 K","volume":"120","author":"Hoshina","year":"2004","journal-title":"J. Chem. Phys."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"7334","DOI":"10.1063\/1.476152","article-title":"Tunneling Chemical Reactions in Solid Parahydrogen: A Case of CD3+H2\u2192CD3H+H at 5K","volume":"108","author":"Momose","year":"1998","journal-title":"J. Chem. Phys."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"13832","DOI":"10.1021\/jp408336n","article-title":"Fourier Transform Infrared Studies of Ammonia Photochemistry in Solid Parahydrogen","volume":"117","author":"Ruzi","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron-Density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"1200","DOI":"10.1139\/p80-159","article-title":"Accurate Spin-Dependent Electron Liquid Correlation Energies for Local Spin Density Calculations: A Critical Analysis","volume":"58","author":"Vosko","year":"1980","journal-title":"Can. J. Phys."},{"key":"ref_41","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2013). Gaussian 09, Revision D.01, Gaussian, Inc."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/22\/5472\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T16:35:53Z","timestamp":1760114153000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/22\/5472"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,11,20]]},"references-count":41,"journal-issue":{"issue":"22","published-online":{"date-parts":[[2024,11]]}},"alternative-id":["molecules29225472"],"URL":"https:\/\/doi.org\/10.3390\/molecules29225472","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2024,11,20]]}}}