{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T02:19:58Z","timestamp":1760235598592,"version":"build-2065373602"},"reference-count":40,"publisher":"MDPI AG","issue":"18","license":[{"start":{"date-parts":[[2021,9,7]],"date-time":"2021-09-07T00:00:00Z","timestamp":1630972800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The conversion of ribonucleosides to 2\u2032-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3\u2032-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSR\u2022\u2212) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)\u2022\u2212 in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)\u2022\u2212 transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)\u2022\u2212 at \u03bbmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104\u2013105 M\u22121s\u22121 at ~22 \u00b0C.<\/jats:p>","DOI":"10.3390\/molecules26185429","type":"journal-article","created":{"date-parts":[[2021,9,7]],"date-time":"2021-09-07T10:24:25Z","timestamp":1631010265000},"page":"5429","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Biomimetic Ketone Reduction by Disulfide Radical Anion"],"prefix":"10.3390","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2916-8654","authenticated-orcid":false,"given":"Sebastian","family":"Barata-Vallejo","sequence":"first","affiliation":[{"name":"Istituto per la Sintesi Organica e la Fotoreattivit\u00e0 (ISOF), Consiglio Nazionale delle Ricerche (CNR), Via P. Gobetti 101, 40129 Bologna, Italy"},{"name":"Departamento de Ciencias Qu\u00edmicas, Facultad de Farmacia y Bioquim\u00edca, Universidad de Buenos Aires, Junin 954, Buenos Aires CP 1113, Argentina"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Konrad","family":"Skotnicki","sequence":"additional","affiliation":[{"name":"Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1359-0869","authenticated-orcid":false,"given":"Carla","family":"Ferreri","sequence":"additional","affiliation":[{"name":"Istituto per la Sintesi Organica e la Fotoreattivit\u00e0 (ISOF), Consiglio Nazionale delle Ricerche (CNR), Via P. Gobetti 101, 40129 Bologna, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8396-0354","authenticated-orcid":false,"given":"Bronislaw","family":"Marciniak","sequence":"additional","affiliation":[{"name":"Center for Advanced Technology, Adam Mickiewicz University, Uniwersytetu Poznanskiego 10, 61-614 Poznan, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7791-9184","authenticated-orcid":false,"given":"Krzysztof","family":"Bobrowski","sequence":"additional","affiliation":[{"name":"Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2626-2925","authenticated-orcid":false,"given":"Chryssostomos","family":"Chatgilialoglu","sequence":"additional","affiliation":[{"name":"Istituto per la Sintesi Organica e la Fotoreattivit\u00e0 (ISOF), Consiglio Nazionale delle Ricerche (CNR), Via P. Gobetti 101, 40129 Bologna, Italy"},{"name":"Center for Advanced Technology, Adam Mickiewicz University, Uniwersytetu Poznanskiego 10, 61-614 Poznan, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,9,7]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Chatgilialoglu, C., Ferreri, C., Geacintov, N.E., Krokidis, M.G., Liu, Y., Masi, A., Shafirovich, V., Terzidis, M.A., and Tsegay, P.S. (2019). 5\u2019,8-Cyclopurine lesions in DNA damage: Chemical, analytical, biological and diagnostic significance. Cells, 8.","DOI":"10.3390\/cells8060513"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"5825","DOI":"10.1021\/jacs.0c00945","article-title":"Oxygen dependent purine lesions in double- stranded oligodeoxynucleotides: Kinetic and computational studies highlight the mechanism for 5\u2019,8-cyplopurine formation","volume":"142","author":"Chatgilialoglu","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Chatgilialoglu, C., Ferreri, C., Krokidis, M.G., Masi, A., and Terzidis, M.A. (2021). On the Relevance of Hydroxyl Radical to Purine DNA Damage. Free Radic. Res.","DOI":"10.1080\/10715762.2021.1876855"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"255","DOI":"10.1021\/cr4002287","article-title":"Lipid Geometrical Isomerism: From Chemistry to Biology and Diagnostics","volume":"114","author":"Chatgilialoglu","year":"2014","journal-title":"Chem. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"191","DOI":"10.1021\/acs.chemrestox.8b00021","article-title":"Trans Lipid Library: Synthesis of Docosahexaenoic Acid (DHA) Monotrans Isomers and Regioisomer Identification in DHA-Containing Supplements","volume":"31","author":"Menounou","year":"2018","journal-title":"Chem. Res. Toxicol."},{"key":"ref_6","doi-asserted-by":"crossref","unstructured":"Vetica, F., Sansone, A., Meliota, C., Batani, G., Roberti, M., Chatgilialoglu, C., and Ferreri, C. (2020). Free Radical-Mediated Formation of Trans-Cardiolipin isomers, Analytical Approaches for Lipidomics and Consequences for the Structural Organization of Membranes. Biomolecules, 10.","DOI":"10.3390\/biom10081189"},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Chatgilialoglu, C., and Studer, A. (2012). Encyclopedia of Radical in Chemistry, Biology and Materials, Wiley.","DOI":"10.1002\/9781119953678"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"2524","DOI":"10.1021\/ar4000407","article-title":"Reversible, Long-Range Radical Transfer in E. coli Class Ia Ribonucleotide Reductase","volume":"46","author":"Minnihan","year":"2013","journal-title":"Acc. Chem. Res."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"16657","DOI":"10.1021\/jacs.7b08192","article-title":"Conformationally Dynamic Radical Transfer within Ribonucleotide Reductase","volume":"139","author":"Greene","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_10","first-page":"1501","article-title":"Radicals Enzymes","volume":"Volume 3","author":"Chatgilialoglu","year":"2012","journal-title":"Encyclopedia of Radical in Chemistry, Biology and Materials"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"8979","DOI":"10.1073\/pnas.96.16.8979","article-title":"High-field EPR detection of a disulfide radical anion in the reduction of cytidine 5\u2019-diphosphate by the E441Q R1 mutant of Escherichia coli ribonucleotide reductase","volume":"96","author":"Lawrence","year":"1999","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"200","DOI":"10.1021\/ja806693s","article-title":"Structure of the Nucleotide Radical Formed during Reaction of CDP\/TTP with the E441Q-\u03b12\u03b22 of E. coli Ribonucleotide Reductase","volume":"131","author":"Zipse","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"4290","DOI":"10.1021\/acs.orglett.8b01713","article-title":"Hydrogen Sulfide: A Reagent for pH-Driven Bioinspired 1,2-Diol Mono-deoxygenation and Carbonyl Reduction in Water","volume":"20","author":"Ferreri","year":"2018","journal-title":"Org. Lett."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1139\/v84-035","article-title":"The effect of pH and complexation on redox reactions between RS radicals and flavins","volume":"62","author":"Ahmad","year":"1984","journal-title":"Can. J. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"5915","DOI":"10.1021\/j100280a091","article-title":"Redox-Potentials of Some Sulfur-Containing Radicals","volume":"90","author":"Surdhar","year":"1986","journal-title":"J. Phys. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"6532","DOI":"10.1021\/j100310a022","article-title":"Reduction Potentials and Exchange Reaction of Thiyl Radicals and Disulfide Anion Radicals","volume":"91","author":"Surdhar","year":"1987","journal-title":"J. Phys. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Chatgilialoglu, C., and Asmus, K.-D. (1990). Applications of Pulse Radiolysis for the Study of Short-lived Sulphur Species. Sulfur-Centered Reactive Intermediates in Chemistry and Biology, Plenum Press.","DOI":"10.1007\/978-1-4684-5874-9"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1411","DOI":"10.1039\/a901155b","article-title":"Disulfide anion radical equilibria: Effects of NH3+, -CO2\u2212, -NHC(O)- and -CH3 groups","volume":"2","author":"Mezyk","year":"1999","journal-title":"J. Chem. Soc. Perkin Trans."},{"key":"ref_19","unstructured":"Sober, H.A. (1970). Handbook of Biochemistry: Selected Data for Molecular Biology, Chemical Rubber Publishing Co.. [2nd ed.]."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"102","DOI":"10.2307\/3579203","article-title":"Determination of the Rate Constant for the Reaction iof Hydroxyl and Oxide Radicals with Cysteine in Aqueous Solution","volume":"145","author":"Mezyk","year":"1996","journal-title":"Radiat. Res."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1016\/0009-2614(95)00100-I","article-title":"Direct rate constant measurement of radical disulphide anion formation for cysteine and cysteamine in aqueous solution","volume":"235","author":"Mezyk","year":"1995","journal-title":"Chem. Phys. Lett."},{"key":"ref_22","unstructured":"Patai, S. (1974). Photochemistry of thiols. The Chemistry of Thiol Group, Wiley. Part 1."},{"key":"ref_23","unstructured":"Turro, N.J. (1991). Modern Molecular Photochemistry, University Science Books."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"3569","DOI":"10.1021\/acs.jpca.5b00302","article-title":"Excited-State Ring-Opening Mechanism of Cyclic Ketones: A MS-CASPT2\/\/CASSCF Study","volume":"119","author":"Xia","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"7112","DOI":"10.1021\/acs.jpca.6b06184","article-title":"Photochemical Reactions of Cyclohexanone: Mechanisms and Dynamics","volume":"120","author":"Shemesh","year":"2016","journal-title":"J. Phys. Chem. A"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2965","DOI":"10.1039\/b110399g","article-title":"H-atom abstraction from thiols by C-centered radicals. A theoretical and experimental study of reaction rates","volume":"4","author":"Reid","year":"2002","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Von Sonntag, C. (2006). Free-Radical-Induced DNA Damage and Its Repair, A Chemical Perspective, Springer.","DOI":"10.1007\/3-540-30592-0"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1283","DOI":"10.1021\/j100629a021","article-title":"Equilibrium and Kinetics of the Acid Dissociation of Several hydroxyalkyl Radicals","volume":"77","author":"Laroff","year":"1973","journal-title":"J. Phys. Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1837","DOI":"10.1021\/ol070593j","article-title":"Compatible Injection and Detection Systems for Studing the Kinetics of Excess Electron Transfer","volume":"9","author":"Xu","year":"2007","journal-title":"Org. Lett."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2819","DOI":"10.1055\/s-0034-1379304","article-title":"Proton-Coupled Electron Transfer in Organic Synthesis: Novel Homolytic Bond Activation and Catalytic Asymmetyric Reactions with Free Radicals","volume":"25","author":"Yayla","year":"2014","journal-title":"Synlett"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2078","DOI":"10.1021\/j100208a035","article-title":"Rate constant for scavenging e\u2212aq in N2O-saturated solutions","volume":"86","author":"Janata","year":"1982","journal-title":"J. Phys. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"5349","DOI":"10.1039\/D0CS00358A","article-title":"Recent advances in the chemistry of ketyl radicals","volume":"50","author":"Agasti","year":"2021","journal-title":"Chem. Soc. Rev."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"399","DOI":"10.1021\/ar00095a002","article-title":"Metal-Ammonia Reductions of Cyclic Aliphatic Ketones","volume":"16","author":"Huffman","year":"1983","journal-title":"Acc. Chem. Res."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"513","DOI":"10.1063\/1.555805","article-title":"Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH\/O\u2212) in aqueous solution","volume":"17","author":"Buxton","year":"1988","journal-title":"J. Phys. Chem. Ref. Data"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"795","DOI":"10.1021\/ja00778a002","article-title":"One-Electron Reduction of the Disulfide Linkage in Aqueous Solution. Formation, Protonation, and Decay Kinetics of the RSSR- Radical","volume":"94","author":"Hoffman","year":"1972","journal-title":"J. Am. Chem. Soc."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"10939","DOI":"10.1039\/C7CP08571K","article-title":"Competition kinetics of OH radical reactions with oxygenated organic compounds in aqueous solution: Rate constants and internal optical absorption effects","volume":"20","author":"Schaefer","year":"2018","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_37","first-page":"S67","article-title":"Free radicals in chemistry, biology, and medicine: Contribution of radiation chemistry","volume":"50","author":"Bobrowski","year":"2005","journal-title":"Nukleonika"},{"key":"ref_38","unstructured":"Mirkowski, J., Wisniowski, P., and Bobrowski, K. (2001). INCT Annual Report 2000, INCT."},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Pedzinski, T., Grzyb, K., Skotnicki, K., Filipiak, P., Bobrowski, K., Chatgilialoglu, C., and Marciniak, B. (2021). Radiation- and Photo-Induced Oxidation Pathways of Methionine in Model Peptide Backbone under Anoxic Conditions. Int. J. Mol. Sci., 22.","DOI":"10.3390\/ijms22094773"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"5532","DOI":"10.1002\/anie.201807247","article-title":"Upconversion of Reductants","volume":"58","author":"Syroeshkin","year":"2019","journal-title":"Angew. Chem. Int. Ed."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/18\/5429\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:57:46Z","timestamp":1760165866000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/18\/5429"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,9,7]]},"references-count":40,"journal-issue":{"issue":"18","published-online":{"date-parts":[[2021,9]]}},"alternative-id":["molecules26185429"],"URL":"https:\/\/doi.org\/10.3390\/molecules26185429","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2021,9,7]]}}}